Microfluidic photoinduced chemical oxidation for Ru(bpy)33+ chemiluminescence - A comprehensive experimental comparison with on-chip direct chemical oxidation.

PubMed

Kadavilpparampu, Afsal Mohammed; Al Lawati, Haider A J; Suliman, Fakhr Eldin O

2017-08-05

For the first time, the analytical figures of merit in detection capabilities of the very less explored photoinduced chemical oxidation method for Ru(bpy) 3 2+ CL has been investigated in detail using 32 structurally different analytes. It was carried out on-chip using peroxydisulphate and visible light and compared with well-known direct chemical oxidation approaches using Ce(IV). The analytes belong to various chemical classes such as tertiary amine, secondary amine, sulphonamide, betalactam, thiol and benzothiadiazine. Influence of detection environment on CL emission with respect to method of oxidation was evaluated by changing the buffers and pH. The photoinduced chemical oxidation exhibited more universal nature for Ru(bpy) 3 2+ CL in detection towards selected analytes. No additional enhancers, reagents, or modification in instrumental configuration were required. Wide detectability and enhanced emission has been observed for analytes from all the chemical classes when photoinduced chemical oxidation was employed. Some of these analytes are reported for the first time under photoinduced chemical oxidation like compounds from sulphonamide, betalactam, thiol and benzothiadiazine class. On the other hand, many of the selected analytes including tertiary and secondary amines such as cetirizine, azithromycin fexofenadine and proline did not produced any analytically useful CL signal (S/N=3 or above for 1μgmL -1 analyte) under chemical oxidation. The most fascinating observations was in the detection limits; for example ofloxacin was 15 times more intense with a detection limit of 5.81×10 -10 M compared to most lowest ever reported 6×10 -9 M. Earlier, penicillamine was detected at 0.1μgmL -1 after derivatization using photoinduced chemical oxidation, but in this study, we improved it to 5.82ngmL -1 without any prior derivatization. The detection limits of many other analytes were also found to be improved by several orders of magnitude under photoinduced chemical oxidation. Copyright © 2017 Elsevier B.V. All rights reserved.

Microfluidic photoinduced chemical oxidation for Ru(bpy)33 + chemiluminescence - A comprehensive experimental comparison with on-chip direct chemical oxidation

NASA Astrophysics Data System (ADS)

Kadavilpparampu, Afsal Mohammed; Al Lawati, Haider A. J.; Suliman, Fakhr Eldin O.

2017-08-01

For the first time, the analytical figures of merit in detection capabilities of the very less explored photoinduced chemical oxidation method for Ru(bpy)32 + CL has been investigated in detail using 32 structurally different analytes. It was carried out on-chip using peroxydisulphate and visible light and compared with well-known direct chemical oxidation approaches using Ce(IV). The analytes belong to various chemical classes such as tertiary amine, secondary amine, sulphonamide, betalactam, thiol and benzothiadiazine. Influence of detection environment on CL emission with respect to method of oxidation was evaluated by changing the buffers and pH. The photoinduced chemical oxidation exhibited more universal nature for Ru(bpy)32 + CL in detection towards selected analytes. No additional enhancers, reagents, or modification in instrumental configuration were required. Wide detectability and enhanced emission has been observed for analytes from all the chemical classes when photoinduced chemical oxidation was employed. Some of these analytes are reported for the first time under photoinduced chemical oxidation like compounds from sulphonamide, betalactam, thiol and benzothiadiazine class. On the other hand, many of the selected analytes including tertiary and secondary amines such as cetirizine, azithromycin fexofenadine and proline did not produced any analytically useful CL signal (S/N = 3 or above for 1 μgmL- 1 analyte) under chemical oxidation. The most fascinating observations was in the detection limits; for example ofloxacin was 15 times more intense with a detection limit of 5.81 × 10- 10 M compared to most lowest ever reported 6 × 10- 9 M. Earlier, penicillamine was detected at 0.1 μg mL- 1 after derivatization using photoinduced chemical oxidation, but in this study, we improved it to 5.82 ng mL- 1 without any prior derivatization. The detection limits of many other analytes were also found to be improved by several orders of magnitude under photoinduced chemical oxidation.

Granzyme B; the chalk-mark of a cytotoxic lymphocyte

PubMed Central

Waterhouse, Nigel J; Sedelies, Karin A; Clarke, Chris JP

2004-01-01

During cytotoxic lymphocyte (CL) mediated killing of target cells, granzyme B is released from the CL into the immune synapse. Recent studies have found that ELISPOT-detection of granzyme B correlated well with conventional assays for CL mediated killing. In this way, the released granzyme B can be used to mark the spot where a target cell was murdered. We discuss the benefits and potential limitations of using this assay to measure CL mediated killing of target cells. PMID:15500699

Simple chemiluminescence determination of ketotifen using tris(1,10 phenanthroline)ruthenium(II)- Ce(IV) system.

PubMed

Mokhtari, Ali; Ghazaeian, Mehrgan; Maghsoudi, Mahdieh; Keyvanfard, Mohsen; Emami, Iraj

2015-11-01

A new method using chemiluminescence (CL) detection has been developed for the simple determination of ketotifen fumarate (KF). The method is based on the catalytic effect of KF in the CL reaction of tris(1,10 phenanthroline)ruthenium(II), Ru(phen)3 (2+), with Ce(IV) in sulfuric acid medium. The CL response was detected using a lab-made chemiluminometer. Effects of chemical variables were investigated and under optimum conditions, the CL intensity was proportional to the concentration of the drug over the range 0.34-34.00 µg mL(-1) KF. The limit of detection (S/N=3) was 0.09 µg mL(-1). Effects of common ingredients were investigated and the method was applied successfully for determining KF in pharmaceutical formulations and human plasma. The percent of relative standard deviation (n=11) at level of 3.4 µg mL(-1) of KF was 4.6% and the minimum sampling rate was 70 samples per hour. The possible CL mechanism is proposed based on the kinetic characteristic of the CL reaction, CL spectrum, UV-Vis and phosphorescence spectra. Copyright © 2015 John Wiley & Sons, Ltd.

Comparison of two methods for selegiline determination: A flow-injection chemiluminescence method using cadmium sulfide quantum dots and corona discharge ion mobility spectrometry.

PubMed

Khataee, Alireza; Lotfi, Roya; Hasanzadeh, Aliyeh; Iranifam, Mortaza; Zarei, Mahmoud; Joo, Sang Woo

2016-01-15

Two analytical approaches including chemiluminescence (CL) and corona discharge ionization ion mobility spectrometry (CD-IMS) were developed for sensitive determination of selegiline (SG). We found that the CL intensity of the KMnO4-Na2S2O3 CL system was significantly enhanced in the presence of L-cysteine capped CdS quantum dots (QDs). A possible CL mechanism for this CL reaction is proposed. In the presence of SG, the enhanced CL system was inhibited. Based on this inhibition, a simple and sensitive flow-injection CL method was proposed for the determination of SG. Under optimum experimental conditions, the decreased CL intensity was proportional to SG concentration in the range of 0.01 to 30.0 mg L(-1). The detection limit (3σ) was 0.004 mg L(-1). Also, SG was determined using CD-IMS, and under optimum conditions of CD-IMS, calibration curves were linear in the range of 0.15 to 42.0 mg L(-1), with a detection limit (3σ) of 0.03 mg L(-1). The precision of the two methods was calculated by analyzing samples containing 5.0 mg L(-1) of SG (n=11). The relative standard deviations (RSDs%) of the flow-injection CL and CD-IMS methods are 2.17% and 3.83%, respectively. The proposed CL system exhibits a higher sensitivity and precision than the CD-IMS method for the determination of SG. Copyright © 2015. Published by Elsevier B.V.

First direct detection limits on sub-GeV dark matter from XENON10.

PubMed

Essig, Rouven; Manalaysay, Aaron; Mardon, Jeremy; Sorensen, Peter; Volansky, Tomer

2012-07-13

The first direct detection limits on dark matter in the MeV to GeV mass range are presented, using XENON10 data. Such light dark matter can scatter with electrons, causing ionization of atoms in a detector target material and leading to single- or few-electron events. We use 15  kg day of data acquired in 2006 to set limits on the dark-matter-electron scattering cross section. The strongest bound is obtained at 100 MeV where σ(e)<3×10(-38)  cm2 at 90% C.L., while dark-matter masses between 20 MeV and 1 GeV are bounded by σ(e)<10(-37)  cm2 at 90% C.L. This analysis provides a first proof of principle that direct detection experiments can be sensitive to dark-matter candidates with masses well below the GeV scale.

Quenching the chemiluminescence of acridinium ester by graphene oxide for label-free and homogeneous DNA detection.

PubMed

He, Yi; Huang, Guangming; Cui, Hua

2013-11-13

It was found that graphene oxide (GO) could effectively quench the chemiluminescence (CL) emission from a acridinium ester (AE)-hydrogen peroxide system. By taking advantage of this quenching effect, as a proof of concept, a label-free and homogeneous DNA assay was developed for the detection of Mycobacterium tuberculosis DNA. In the absence of target DNA, both probe DNA and AE were absorbed on the surface of GO, producing a weak CL emission owing to the CL quenching effect of GO. However, in the presence of target DNA, a double-stranded structure of DNA was generated, leading to the release of the oligonucleotide from the GO surface. AE favors binding with double-stranded DNA, which will be released from the GO surface; thus, the quenching effect of GO will be no longer effective and a strong CL signal can be observed. This assay can detect M. tuberculosis DNA with a detection limit of 0.65 nM. This sensitivity is lower than that of previously reported electrochemical detection.

Preparation of an Efficient Ratiometric Fluorescent Nanoprobe (m-CDs@[Ru(bpy)3]2+) for Visual and Specific Detection of Hypochlorite on Site and in Living Cells.

PubMed

Zhan, Yuanjin; Luo, Fang; Guo, Longhua; Qiu, Bin; Lin, Yuhong; Li, Juan; Chen, Guonan; Lin, Zhenyu

2017-11-22

Hypochlorite (ClO - ) is one of the most important reactive oxygen species (ROS), which plays an important role in sustaining human innate immunity during microbial invasion. Moreover, ClO - is a powerful oxidizer for water treatment. The safety of drinking water is closely related to its content. Herein, m-phenylenediamine (mPD) is used as a precursor to prepare carbon dots (named m-CDs) with highly fluorescent quantum yield (31.58% in water), and our investigation shows that the strong fluorescent emission of m-CDs can be effectively quenched by ClO - . Based on these findings, we developed a novel fluorescent nanoprobe (m-CDs) for highly selective detection of ClO - . The linear range was from 0.05 to 7 μM (R 2 = 0.998), and the limit of detection (S/N = 3) was as low as 0.012 μM. Moreover, a portable agarose hydrogel solid matrix-based ratiometric fluorescent nanoprobe (m-CDs@[Ru(bpy) 3 ] 2+ ) sensor was subsequently developed for visual on-site detection of ClO - with the naked eyes under a UV lamp, suggesting its potential in practical application with low cost and excellent performance in water quality monitoring. Additionally, intracellular detection of exogenous ClO - was demonstrated via ratiometric imaging microscopy.

Simple and rapid chemiluminescence aptasensor for Hg2+ in contaminated samples: A new signal amplification mechanism.

PubMed

Qi, Yingying; Xiu, Fu-Rong; Yu, Gending; Huang, Lili; Li, Baoxin

2017-01-15

Detection of ultralow concentration of heavy metal ion Hg 2+ is important for human health protection and environment monitoring because of the gradual accumulation in environmental and biological fields. Herein, we report a convenient chemiluminescence (CL) biosensing platform for ultrasensitive Hg 2+ detection by signal amplification mechanism from positively charged gold nanoparticles ((+)AuNPs). It is based on (+)AuNPs charge effect and aptamer conformation change induced by target to stimulate the generation of CL in the presence of H 2 O 2 and luminol without high salt medium. Notably particularly, the typical problem of the high salt medium from (-) AuNPs system, like influencing aptamers' bind with target and hindering CL reaction can be effectively addressed through the direct introduction of (+)AuNPs. Therefore, the proposed biosensing exhibits a high sensitivity toward target Hg 2+ with a detection limit of 16 pM, which is far below the limit (10nM) defined by the U.S. Environmental Protection Agency in drinkable water, and is about 10-fold lower than the previously reported aptamer-based assays for Hg 2+ . This sensing platform provides a simple, rapid, and cost-effective approach for label-free sensitive detection of Hg 2+ . Moreover, it is universal for the detection of other targets. Undoubtedly, such a direct utilizing of (+)AuNPs' charge effect will provide a new signal amplification way for label-free aptamer-based CL analysis. Copyright © 2016 Elsevier B.V. All rights reserved.

Capillary electrophoresis-chemiluminescence detection for carcino-embryonic antigen based on aptamer/graphene oxide structure.

PubMed

Zhou, Zi-Ming; Feng, Zhe; Zhou, Jun; Fang, Bi-Yun; Qi, Xiao-Xiao; Ma, Zhi-Ya; Liu, Bo; Zhao, Yuan-Di; Hu, Xue-Bin

2015-02-15

A new strategy is proposed for determination of carcino-embryonic antigen (CEA) based on aptamer/graphene oxide (Apt/GO) by capillary electrophoresis-chemiluminescence (CE-CL) detection system. CEA aptamer conjugated with horseradish peroxidase (HRP) firstly mixes with GO, and the CL will be quenched because the stack of HRP-Apt on GO leads to chemiluminescence resonance energy transfer (CRET). When CEA exists, the specific combination of HRP-Apt and CEA can form HRP-Apt-CEA complex, which dissociates from GO. Then, the CL catalyzed by HRP-Apt-CEA complex can be detected without any CRET, and the content of CEA can be estimated by the CL intensity. It has been proved that the interference issue resulted from free HRP-Apt is solved well by mixing GO firstly with HRP-Apt, which blocks the free HRP-Apt's CL signal due to CL quenching effect of GO; and the interference resulted from GO to CL is also solved by CE, then the sensitivity and accuracy can be greatly improved. Results also showed that the CL intensity had a linear relationship with the concentration of CEA in the range from 0.0654 to 6.54 ng/mL, and the limit of detection was approximately 4.8 pg/mL (S/N = 3). This proposed method with high specificity offers a new way for separation and determination of biomolecule, and has good potential in application of biochemistry and bioanalysis. Copyright © 2014 Elsevier B.V. All rights reserved.

Development of carbon dots modified fluorescent molecular imprinted Polymer@Ag/AgCl nanoparticle for hepatocellular carcinoma marker

NASA Astrophysics Data System (ADS)

Karfa, Paramita; Madhuri, Rashmi; Sharma, Prashant K.

2017-05-01

In this work, a sensitive and selective fluorescent molecularly imprinted polymer (MIP) was developed for detection of hepatocellular carcinoma (HCC) biomarker i.e. alpha feto protein (AFP) using Ag/AgCl as platform. Here, the carbon dots and Ag/AgCl nanoparticles were functionalized with vinyl groups and used as functional monomer for synthesis of AFP-imprinted polymer. The imprinted polymer shows a linear range of 3.96 ng mL-1 to 80.0 ng mL-1 with detection limit of 0.42 ng mL-1.The adsorption property of the MIP@Ag/AgCl was studied and shows the high affinity binding towards their target analyte without any cross-reactivity and false-positive or false-negative results.

An Observational Upper Limit on the Interstellar Number Density of Asteroids and Comets

NASA Astrophysics Data System (ADS)

Engelhardt, Toni; Jedicke, Robert; Vereš, Peter; Fitzsimmons, Alan; Denneau, Larry; Beshore, Ed; Meinke, Bonnie

2017-03-01

We derived 90% confidence limits (CLs) on the interstellar number density ({ρ }{IS}{CL}) of interstellar objects (ISOs; comets and asteroids) as a function of the slope of their size-frequency distribution (SFD) and limiting absolute magnitude. To account for gravitational focusing, we first generated a quasi-realistic ISO population to ˜ 750 {au} from the Sun and propagated it forward in time to generate a steady state population of ISOs with heliocentric distance < 50 {au}. We then simulated the detection of the synthetic ISOs using pointing data for each image and average detection efficiencies for each of three contemporary solar system surveys—Pan-STARRS1, the Mt. Lemmon Survey, and the Catalina Sky Survey. These simulations allowed us to determine the surveys’ combined ISO detection efficiency under several different but realistic modes of identifying ISOs in the survey data. Some of the synthetic detected ISOs had eccentricities as small as 1.01, which is in the range of the largest eccentricities of several known comets. Our best CL of {ρ }{IS}{CL}=1.4× {10}-4 {{au}}-3 implies that the expectation that extra-solar systems form like our solar system, eject planetesimals in the same way, and then distribute them throughout the Galaxy, is too simplistic, or that the SFD or behavior of ISOs as they pass through our solar system is far from expectation.

A novel dual-ratiometric-response fluorescent probe for SO2/ClO- detection in cells and in vivo and its application in exploring the dichotomous role of SO2 under the ClO- induced oxidative stress.

PubMed

Dou, Kun; Fu, Qiang; Chen, Guang; Yu, Fabiao; Liu, Yuxia; Cao, Ziping; Li, Guoliang; Zhao, Xianen; Xia, Lian; Chen, Lingxin; Wang, Hua; You, Jinmao

2017-07-01

Intracellular reactive sulfur species and reactive oxygen species play vital roles in immunologic mechanism. As an emerging signal transmitter, SO 2 can be generated as the anti-oxidant, while SO 2 is also a potential oxidative stress-inducer in organism. Aiming to elucidate in-depth the dichotomous role of SO 2 under oxidative stress, we designed a dual-response fluorescent probe that enabled the respective or successive detection of SO 2 and ClO - . The probe itself emits the red fluorescence (625 nm) which can largely switch to blue (410 nm) and green fluorescence (500 nm) respectively in response to SO 2 and ClO - , allowing the highly selective and accurate ratiometric quantification for both SO 2 and ClO - in cells. Moreover the ultrafast (SO 2 : <60 s; ClO - : within sec) and highly sensitive (detection limits: SO 2 : 3.5 nM; ClO - : 12.5 nM) detection were achieved. With the robust applicability, the developed probe was successfully used to quantify SO 2 and endogenous ClO - in respectively the HeLa cells and the RAW 264.7 cells, as well as to visualize the dynamic of SO 2 /ClO - in zebrafish. The fluorescent imaging studies and flow cytometry analysis confirmed the burst-and-depletion and meanwhile the oxidative-and-antioxidative effects of intracellular SO 2 under the NaClO induced oxidative stress. Copyright © 2017 Elsevier Ltd. All rights reserved.

Pre-evaluation of metal ions as a catalyst on chemiluminometric sequential injection analysis with luminol-H2O2 system.

PubMed

Takayanagi, Toshio; Inaba, Yuya; Kanzaki, Hiroyuki; Jyoichi, Yasutaka; Motomizu, Shoji

2009-09-15

Catalytic effect of metal ions on luminol chemiluminescence (CL) was investigated by sequential injection analysis (SIA). The SIA system was set up with two solenoid micropumps, an eight-port selection valve, and a photosensor module with a fountain-type chemiluminescence cell. The SIA system was controlled and the CL signals were collected by a LabVIEW program. Aqueous solutions of luminol, H(2)O(2), and a sample solution containing metal ion were sequentially aspirated to the holding coil, and the zones were immediately propelled to the detection cell. After optimizing the parameters using 1 x 10(-5)M Fe(3+) solution, catalytic effect of some metal species was compared. Among 16 metal species examined, relatively strong CL responses were obtained with Fe(3+), Fe(2+), VO(2+), VO(3)(-), MnO(4)(-), Co(2+), and Cu(2+). The limits of detection by the present SIA system were comparable to FIA systems. Permanganate ion showed the highest CL sensitivity among the metal species examined; the calibration graph for MnO(4)(-) was linear at the concentration level of 10(-8)M and the limit of detection for MnO(4)(-) was 4.0 x 10(-10)M (S/N=3).

Calibration of the Fluorine, Chlorine and Hydrogen Content of Apatites With the ChemCam LIBS Instrument

NASA Technical Reports Server (NTRS)

Meslin, P.-Y.; Cicutto, L.; Forni, O.; Drouet, C.; Rapin, W.; Nachon, M.; Cousin, A.; Blank, J. G.; McCubbin, F. M.; Gasnault, O.;

Determination of bromine, chlorine and iodine in environmental aqueous samples by epithermal neutron activation analysis and Compton suppression

USGS Publications Warehouse

Landsberger, S.; O'Kelly, D. J.; Braisted, J.; Panno, S.

2006-01-01

Halides, particularly Br- and Cl-, have been used as indicators of potential sources of Na+ and Cl- in surface water and groundwater with limited success. Contamination of groundwater and surface water by Na+ and Cl- is a common occurrence in growing urban areas and adversely affects municipal and private water supplies in Illinois and other states, as well as vegetation in environmentally sensitive areas. Neutron activation analysis (NAA) can be effectively used to determine these halogens, but often the elevated concentrations of sodium and chlorine in water samples can give rise to very high detection limits for bromine and iodine due to elevated backgrounds from the activation process. We present a detailed analytical scheme to determine Cl, Br and I in aqueous samples with widely varying Na and Cl concentrations using epithermal NAA in conjunction with Compton suppression. ?? 2006 Akade??miai Kiado??.

Determination of NH(3) gas by combination of nanosized LaCoO(3) converter with chemiluminescence detector.

PubMed

Shi, Jinjun; Yan, Ruoxue; Zhu, Yongfa; Zhang, Xinrong

2003-10-17

Combination of a novel NH(3) converter based on nanosized materials with chemiluminescence (CL) detector for the determination of NH(3) gas was demonstrated in this paper. NH(3) gas is oxidized on different nanosized catalysts to produce NO(x), which can react with luminol to generate CL emission. Eight nanosized materials were investigated as catalyst, and CL was detected from seven of them. The nanosized LaCoO(3) was chosen as the catalyst for preparing the converter because of its higher activity than others. Under the optimized conditions, the linear range of CL intensity versus concentration of NH(3) gas is 0.04-10 ppm (r=0.9951, n=14) with the detection limit of 0.014 ppm. The method offers advantages of long lifetime of the converter, fast response and high selectivity to NH(3). There was no response while the foreign substances, such as hydrogen, oxygen, nitrogen, formaldehyde, acetone and gasoline passing through the CL detection system, and the interference of CCl(4), ethanol, ethylene and toluene was insignificant.

Is there any chlorine monoxide in the stratosphere?

NASA Technical Reports Server (NTRS)

Rogers, J. D.; Mumma, M. J.; Kostiuk, T.; Deming, D.; Hillman, J. J.; Faris, J.; Zipoy, D.

1982-01-01

A ground based search for the 856.50137/cm R(9.5) and for the 859.76765 R(12.5) transitions of stratospheric (Cl-35)O was made in the solar absorption mode using an infrared heterodyne spectrometer. Lines due to stratospheric HNO3 and tropospheric OCS were detected, at about 0.3% absorption levels. The expected lines of ClO in this same region were not detected, even though the optical depth of the ClO lines should be on the order of 0.2% using currently accepted ClO abundances. These infrared measurements suggest that stratospheric ClO is at least a factor of 7 less abundant than is indicated by indirect in situ fluorescence measurements, and the upper limit of 2.4x10 to the 13th power molecules/sq cm to the integrated column density of ClO is a factor of over 4 less than is indicted by microwave measurements. Results imply that the release of fluorocarbon precursors of ClO may be significantly less important for the destruction of stratospheric ozone than was previously thought.

Gold nanoclusters-based chemiluminescence resonance energy transfer method for sensitive and label-free detection of trypsin.

PubMed

You, Xiaoying; Li, Yinhuan; Li, Baoping; Ma, Jie

2016-01-15

A chemiluminescence resonance energy transfer (CRET) platform was developed for sensitive and label-free detection of protease by using trypsin as a model analyte. In this CRET platform, bis(2,4,6-trichlorophenyl)oxalate-hydrogen peroxide chemiluminescence (CL) reaction was utilized as an energy donor and bovine serum albumin (BSA)-stabilized gold nanoclusters (Au NCs) as an energy acceptor. The BSA-stabilized Au NCs triggered the CRET phenomenon by accepting the energy from TCPO-H2O2 CL reaction, thus producing intense CL. In the presence of trypsin, the protein template of BSA-stabilized Au NCs was digested, which frustrated the energy transfer efficiency between the CL donor and the BSA-stabilized Au NCs, leading to a significant decrease in the CL signal. The decreased CL signal was proportional to the logarithm of trypsin concentration in the range of 0.01-50.0µg mL(-1). The detection limit for trypsin was 9ng mL(-)(1) and the relative standard deviations were lesser than 3% (n=11). This Au NCs-based CRET platform was successfully applied to the determination of trypsin in human urine samples, demonstrating its potential application in clinical diagnosis. Copyright © 2015 Elsevier B.V. All rights reserved.

Gold nanoparticles hosted in a water-soluble silsesquioxane polymer applied as a catalytic material onto an electrochemical sensor for detection of nitrophenol isomers.

PubMed

Silva, Paulo Sérgio da; Gasparini, Bianca C; Magosso, Hérica A; Spinelli, Almir

2014-05-30

The water-soluble 3-n-propyl-4-picolinium silsesquioxane chloride (Si4Pic(+)Cl(-)) polymer was prepared, characterized and used as a stabilizing agent for the synthesis of gold nanoparticles (nAu). The ability of Si4Pic(+)Cl(-) to adsorb anionic metal complexes such as AuCl4(-) ions allowed well-dispersed nAu to be obtained with an average particle size of 4.5nm. The liquid suspension of nAu-Si4Pic(+)Cl(-) was deposited by the drop coating method onto a glassy carbon electrode (GCE) surface to build a sensor (nAu-Si4Pic(+)Cl(-)/GCE) which was used for the detection of o-nitrophenol (o-NP) and p-nitrophenol (p-NP). Under optimized experimental conditions the reduction peak current increased with increasing concentrations of both nitrophenol isomers in the range of 0.1-1.5μmolL(-1). The detection limits were 46nmolL(-1) and 55nmolL(-1) for o-NP and p-NP, respectively. These findings indicate that the nAu-Si4Pic(+)Cl(-) material is a very promising candidate to assemble electrochemical sensors for practical applications in the field of analytical chemistry. Copyright © 2014 Elsevier B.V. All rights reserved.

Flow-injection chemiluminescent determination of estrogen benzoate using the tris(1,10-phenanthroline) ruthenium(II)-permanganate system.

PubMed

Ma, Yan; Cao, Wei; Qiao, Shuang; Liu, Wenwen; Yang, Jinghe

2011-01-01

Chemiluminescence (CL) detection for the determination of estrogen benzoate, using the reaction of tris(1,10-phenanthroline)ruthenium(II)-Na(2)SO(3)-permanganate, is described. This method is based on the CL reaction of estrogen benzoate (EB) with acidic potassium permanganate and tris(1,10-phenanthroline)ruthenium(II). The CL intensity is greatly enhanced when Na(2)SO(3) is added. After optimization of the different experimental parameters, a calibration graph for estrogen benzoate is linear in the range 0.05-10 µg/mL. The 3 s limit of detection is 0.024 µg/mL and the relative standard deviation was 1.3% for 1.0 µg/mL estrogen benzoate (n = 11). This proposed method was successfully applied to commercial injection samples and emulsion cosmetics. The mechanism of CL reaction was also studied. Copyright © 2011 John Wiley & Sons, Ltd.

Cl atom recombination on silicon oxy-chloride layers deposited on chamber walls in chlorine-oxygen plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khare, Rohit; Srivastava, Ashutosh; Donnelly, Vincent M.

2012-09-15

Chlorine atom recombination coefficients were measured on silicon oxy-chloride surfaces deposited in a chlorine inductively coupled plasma (ICP) with varying oxygen concentrations, using the spinning wall technique. A small cylinder embedded in the walls of the plasma reactor chamber was rapidly rotated, repetitively exposing its surface to the plasma chamber and a differentially pumped analysis chamber housing a quadruple mass spectrometer for line-of-sight desorbing species detection, or an Auger electron spectrometer for in situ surface analysis. The spinning wall frequency was varied from 800 to 30 000 rpm resulting in a detection time, t (the time a point on themore » surface takes to rotate from plasma chamber to the position facing the mass or Auger spectrometer), of {approx}1-40 ms. Desorbing Cl{sub 2}, due to Langmuir-Hinshelwood (LH) Cl atom recombination on the reactor wall surfaces, was detected by the mass spectrometer and also by a pressure rise in one of the differentially pumped chambers. LH Cl recombination coefficients were calculated by extrapolating time-resolved desorption decay curves to t = 0. A silicon-covered electrode immersed in the plasma was either powered at 13 MHz, creating a dc bias of -119 V, or allowed to electrically float with no bias power. After long exposure to a Cl{sub 2} ICP without substrate bias, slow etching of the Si wafer coats the chamber and spinning wall surfaces with an Si-chloride layer with a relatively small amount of oxygen (due to a slow erosion of the quartz discharge tube) with a stoichiometry of Si:O:Cl = 1:0.38:0.38. On this low-oxygen-coverage surface, any Cl{sub 2} desorption after LH recombination of Cl was below the detection limit. Adding 5% O{sub 2} to the Cl{sub 2} feed gas stopped etching of the Si wafer (with no rf bias) and increased the oxygen content of the wall deposits, while decreasing the Cl content (Si:O:Cl = 1:1.09:0.08). Cl{sub 2} desorption was detectable for Cl recombination on the spinning wall surface coated with this layer, and a recombination probability of {gamma}{sub Cl} = 0.03 was obtained. After this surface was conditioned with a pure oxygen plasma for {approx}60 min, {gamma}{sub Cl} increased to 0.044 and the surface layer was slightly enriched in oxygen fraction (Si:O:Cl = 1:1.09:0.04). This behavior is attributed to a mechanism whereby Cl LH recombination occurs mainly on chlorinated oxygen sites on the silicon oxy-chloride surface, because of the weak Cl-O bond compared to the Cl-Si bond.« less

Distribution, bioaccumulation and trophic transfer of chlorinated polyfluoroalkyl ether sulfonic acids in the marine food web of Bohai, China.

PubMed

Chen, Hong; Han, Jianbo; Cheng, Jiayi; Sun, Ruijun; Wang, Xiaomeng; Han, Gengchen; Yang, Wenchao; He, Xin

2018-06-04

Chlorinated polyfluoroalkyl ether sulfonic acids (Cl-PFESAs) caused great concerns recently as novel fluorinated alternatives. However, information on their bioconcentration, bioaccumulation and biomagnification in marine ecosystems is limited. In this study, 152 biological samples including invertebrates, fishes, seabirds and mammals collected from Bohai Sea of China were analyzed to investigate the residual level, spatial distribution, bioaccumulation and biomagnification of Cl-PFESAs. 6:2 Cl-PFESA was found in concentrations ranging from

Determination of phenformin hydrochloride using molecular imprinting technology coupled with flow-injection chemiluminescence.

PubMed

Liu, Zhenbo; Jia, Fengyan; Wang, Wenwen; Wang, Cuixia; Liu, Yongming

2012-01-01

A novel method was developed using molecular imprinting technology (MIT) coupled with flow-injection chemiluminescence (FI-CL) for highly sensitive detection of phenformin hydrochloride (PH). The phenformin imprinted polymer was synthesized with methacrylic acid (MAA) as a functional monomer and ethylene glycol dimethacrylate (EGDMA) as a cross-linker. Newly synthesized molecularly imprinted polymer (MIP) particles were packed into a column as a selective recognition element for determination of PH. A CL method for the determination of PH was developed based on the CL reaction of PH with N-bromosuccinimide sensitized by eosin Y in basic media. The optimization of detection conditions was investigated. The CL intensity responded linearly to the concentration of PH in the range 0.09-2.0 µg/mL, with a correlation coefficient of 0.9920. The detection limit was 0.031 µg/mL. The relative standard deviation for the determination of 1.0 µg/mL PH solution was 1.0% (n = 11). The method was applied to the determination of PH in urine samples, with satisfactory results. Copyright © 2011 John Wiley & Sons, Ltd.

Mass spectrometer characterization of halogen gases in air at atmospheric pressure.

PubMed

Ivey, Michelle M; Foster, Krishna L

2005-03-01

We have developed a new interface for a commercial ion trap mass spectrometer equipped with APCI capable of real-time measurements of gaseous compounds with limits of detection on the order of pptv. The new interface has been tested using the detection of Br2 and Cl2 over synthetic seawater ice at atmospheric pressure as a model system. A mechanical pump is used to draw gaseous mixtures through a glass manifold into the corona discharge area, where the molecules are ionized. Analysis of bromine and chlorine in dry air show that ion intensity is affected by the pumping rate and the position of the glass manifold. The mass spectrometer signals for Br2 are linear in the 0.1-10.6 ppbv range, and the estimated 3sigma detection limit is 20 pptv. The MS signals for Cl2 are linear in the 0.2-25 ppbv range, and the estimated 3sigma detection limit is 1 ppbv. This new interface advances the field of analytical chemistry by introducing a practical modification to a commercially available ion trap mass spectrometer that expands the available methods for performing highly specific and sensitive measurements of gases in air at atmospheric pressure.

Speciation of inorganic and organolead compounds by gas chromatography-atomic absorption spectrometry and the determination of lead species after pre-concentration onto diphenylthiocarbazone-anchored polymeric microbeads

NASA Astrophysics Data System (ADS)

Salih, Bekir

2000-07-01

Poly(EGDMA-HEMA) microbeads were prepared by suspension copolymerization of ethyleneglycol dimethacrylate (EGDMA) and hydroxyethylmethacrylate (HEMA) using poly(vinylalcohol), benzoyl peroxide and toluene as the stabilizer, the initiator, and the diluent, respectively. A chelating ligand, diphenylthiocarbazone (dithizone), was then attached. The microbeads were characterized by FT-IR and elemental analysis. The affinity microbeads containing 118.9 μmol dithizone g -1 polymer were used in the adsorption/desorption of some selected lead species, Pb(II), (CH 3) 2PbCl 2, (C 2H 5) 2PbCl 2, (CH 3) 3PbCl, and (C 2H 5) 3PbCl from aqueous media containing different amounts of these species (5-200 mg l -1) at different pH values, 2.0-8.0. Adsorption rates were high, and adsorption equilibrium was reached in approximately 45 min. The detection limits of the lead species onto the dithizone-anchored affinity microbeads from solutions containing a single species was 0.28 ng ml -1 for Pb(II), 0.12 ng ml -1 for (CH 3) 3PbCl, 0.24 ng ml -1 for (C 2H 5) 3PbCl, 0.18 ng ml -1 for (CH 3) 2PbCl 2 and 0.30 ng ml -1 for (C 2H 5) 2PbCl 2 on a weight basis for lead. The same behavior was observed during competitive adsorption that is adsorption from a mixture. The affinity order of the lead species was Pb(II)>(CH 3) 2PbCl 2>(CH 3) 3PbCl>(C 2H 5) 3PbCl>(C 2H 5) 2PbCl 2 for competitive adsorption. Dithizone-anchored microbeads were found to be suitable for repeated use of more than five cycles, without noticeable loss of adsorption capacity. For the speciation of organolead compounds, ionic alkyllead compounds were derivatized by n-butyl Grignard reagent and the speciation was performed using a gas chromatography-atomic absorption spectrometry coupled system. Detection limits were improved at least 180-fold with this preconcentration approach using the dithizone-anchored microbeads.

A cascade amplification strategy based on rolling circle amplification and hydroxylamine amplified gold nanoparticles enables chemiluminescence detection of adenosine triphosphate.

PubMed

Wang, Ping; Zhang, Tonghuan; Yang, Taoyi; Jin, Nan; Zhao, Yanjun; Fan, Aiping

2014-08-07

A highly sensitive and selective chemiluminescent (CL) biosensor for adenosine triphosphate (ATP) was developed by taking advantage of the ATP-dependent enzymatic reaction (ATP-DER), the powerful signal amplification capability of rolling circle amplification (RCA), and hydroxylamine-amplified gold nanoparticles (Au NPs). The strategy relies on the ability of ATP, a cofactor of T4 DNA ligase, to trigger the ligation-RCA reaction. In the presence of ATP, the T4 DNA ligase catalyzes the ligation reaction between the two ends of the padlock probe, producing a closed circular DNA template that initiates the RCA reaction with phi29 DNA polymerase and dNTP. Therein, many complementary copies of the circular template can be generated. The ATP-DER is eventually converted into a detectable CL signal after a series of processes, including gold probe hybridization, hydroxylamine amplification, and oxidative gold metal dissolution coupled with a simple and sensitive luminol CL reaction. The CL signal is directly proportional to the ATP level. The results showed that the detection limit of the assay is 100 pM of ATP, which compares favorably with those of other ATP detection techniques. In addition, by taking advantage of ATP-DER, the proposed CL sensing system exhibits extraordinary specificity towards ATP and could distinguish the target molecule ATP from its analogues. The proposed method provides a new and versatile platform for the design of novel DNA ligation reaction-based CL sensing systems for other cofactors. This novel ATP-DER based CL sensing system may find wide applications in clinical diagnosis as well as in environmental and biomedical fields.

CE with chemiluminescence detection for the determination of thyroxine in human serum.

PubMed

Mu, Xiaomei; Li, Shuting; Lu, Xin; Zhao, Shulin

2014-04-01

A sensitive and rapid approach to perform thyroxine (T4) assay by CE with chemiluminescence (CL) detection was developed. The sensitive detection was based on the enhancement effect of T4 on the CL reaction between luminol and potassium permanganate (KMnO4 ) in alkaline solution. A laboratory-built reaction flow cell and a photon counter were deployed for the CL detection. Experimental conditions for CL detection were studied in detail to achieve maximum assay sensitivity. Optimal conditions were found to be 5.0 × 10(-4) M luminol added to the CE running buffer and 9.2 × 10(-5) M KMnO4 in 0.072 M NaOH solution introduced postcolumn. In the optimized experimental conditions, the linear range for T4 detection was 6.0 × 10(-8) -6.0 × 10(-6) M, with the detection limit of 2.0 × 10(-8) M (S/N = 3). Six human serum samples from healthy subjects, hyperthyroid patients and hypothyroid patients were analyzed by the presented method. The serum level of T4 in healthy subjects was found be 9.0 × 10(-8) M, whereas the T4 level was found to be 15.6 × 10(-8) M in hyperthyroid patients and 1.3 × 10(-8) M in hypothyroid patients. The results suggested a potential application of the proposed assay in rapid primary diagnosis of diseases such as hyperthyroid and hypothyroid. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of the rotating cylinder electrode in molten LiCl-KCl eutectic containing uranium(III)- and magnesium(II)-chloride

NASA Astrophysics Data System (ADS)

Rappleye, Devin; Simpson, Michael F.

2017-04-01

The application of the rotating cylinder electrode (RCE) to molten LiCl-KCl eutectic mixtures for electroanalytical measurements is presented. This enabled the measurement of the limiting current which was observed to follow a linear trend with the rotational rate raised to 0.64-0.65 power on average, which closely agrees with existing RCE mass-transfer correlations. This is the first publication of electroanalytical RCE measurements in LiCl-KCl eutectic based molten salt mixtures, to our knowledge. These measurements were made in mixtures of molten LiCl-KCl eutectic containing UCl3 and MgCl2. Kinetic parameters were calculated for Mg2+ in LiCl-KCl eutectic. The exchange current density (io) of Mg2+ deposition varied with mole fraction (x) according to io(A cm-2) = 1.64x0.689. The parameters from RCE measurements were also applied in an electrochemical co-deposition model entitled DREP to detect and predict the deposition rate of U and Mg. DREP succeeded in detecting the co-deposition of U and Mg, even when Mg constituted less than 0.5 wt% of the deposit.

Determination of the pseudoephedrine content in pharmaceutical formulations and in biological fluids using a microbore HPLC system interfaced to a microfluidic chemiluminescence detector.

PubMed

Kadavilpparampu, Afsal Mohammed; Al-Lawati, Haider A J; Suliman, FakhrEldin O; Al Kindy, Salma M Z

2015-12-01

A novel automated precolumn derivatization followed by separation using liquid chromatography for the determination of pseudoephedrine (PSE) by a microfluidic chemiluminescence detector has been developed. An on-line derivatization procedure was utilized by converting PSE into a highly light emitting species in a Ru(bipy)3(2+)-peroxydisulphate chemiluminescence (CL) system by derivatizing it with a 1.0 M formaldehyde solution. The derivatized analyte was directly injected into a microbore high-performance liquid chromatography (HPLC) system coupled to an on-chip chemiluminescence detector. The newly developed highly selective, sensitive and fast HPLC-CL method was validated and successfully applied for the analysis of PSE in pharmaceutical formulations and a human urine sample. The selectivity of the method is not only due to the HPLC separation but is also due to the highly selective detection principle of the Ru(bipy)3(2+)-peroxydisulphate CL system used. There was no interference observed from the common preservatives and excipients used in pharmaceutical preparations, which did not show any significant CL signal. The retention time of PSE was less than 3 min, and the detection limits and quantification limits were found to be 5.7 and 26.0 µg L(-1), respectively. Copyright © 2015 John Wiley & Sons, Ltd.

Effect of gold nanoparticle as a novel nanocatalyst on luminol-hydrazine chemiluminescence system and its analytical application.

PubMed

Safavi, A; Absalan, G; Bamdad, F

2008-03-10

In this work the catalytic role of unsupported gold nanoparticles on the luminol-hydrazine reaction is investigated. Gold nanoparticles catalyze the reaction of hydrazine and dissolved oxygen to generate hydrogen peroxide and also catalyze the oxidation of luminol by the produced hydrogen peroxide. The result is an intense chemiluminescence (CL) due to the excited 3-aminophthalate anion. In the absence of gold nanoparticles no detectable CL was observed by the reaction of luminol and hydrazine unless an external oxidant is present in the system. The size effect of gold nanoparticles on the CL intensity was investigated. The most intensive CL signals were obtained with 15-nm gold nanoparticles. UV-vis spectra and transmission electron microscopy studies were used to investigate the CL mechanism. The luminol and hydroxide ion concentration, gold nanoparticles size and flow rate were optimized. The proposed method was successfully applied to the determination of hydrazine in boiler feed water samples. Between 0.1 and 30 microM of hydrazine could be determined with a detection limit of 30 nM.

Electrochemical Co-Reduction Synthesis of AuPt Bimetallic Nanoparticles-Graphene Nanocomposites for Selective Detection of Dopamine in the Presence of Ascorbic Acid and Uric Acid

PubMed Central

Zhao, Zongya; Zhang, Mingming; Chen, Xiang; Li, Youjun; Wang, Jue

2015-01-01

In this paper, AuPt bimetallic nanoparticles-graphene nanocomposites were obtained by electrochemical co-reduction of graphene oxide (GO), HAuCl4 and H2PtCl6. The as-prepared AuPt bimetallic nanoparticles-graphene nanocomposites were characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and other electrochemical methods. The morphology and composition of the nanocomposite could be easily controlled by adjusting the HAuCl4/H2PtCl6 concentration ratio. The electrochemical experiments showed that when the concentration ratio of HAuCl4/H2PtCl6 was 1:1, the obtained AuPt bimetallic nanoparticles-graphene nanocomposite (denoted as Au1Pt1NPs-GR) possessed the highest electrocatalytic activity toward dopamine (DA). As such, Au1Pt1NPs-GR nanocomposites were used to detect DA in the presence of ascorbic acid (AA) and uric acid (UA) using the differential pulse voltammetry (DPV) technique and on the modified electrode, there were three separate DPV oxidation peaks with the peak potential separations of 177 mV, 130 mV and 307 mV for DA and AA, DA and UA, AA and UA, respectively. The linear range of the constructed DA sensor was from 1.6 μM to 39.7 μM with a detection limit of 0.1 μM (S/N = 3). The obtained DA sensor with good stability, high reproducibility and excellent selectivity made it possible to detect DA in human urine samples. PMID:26184200

Electrochemical Co-Reduction Synthesis of AuPt Bimetallic Nanoparticles-Graphene Nanocomposites for Selective Detection of Dopamine in the Presence of Ascorbic Acid and Uric Acid.

PubMed

Zhao, Zongya; Zhang, Mingming; Chen, Xiang; Li, Youjun; Wang, Jue

2015-07-09

In this paper, AuPt bimetallic nanoparticles-graphene nanocomposites were obtained by electrochemical co-reduction of graphene oxide (GO), HAuCl4 and H2PtCl6. The as-prepared AuPt bimetallic nanoparticles-graphene nanocomposites were characterized by scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and other electrochemical methods. The morphology and composition of the nanocomposite could be easily controlled by adjusting the HAuCl4/H2PtCl6 concentration ratio. The electrochemical experiments showed that when the concentration ratio of HAuCl4/H2PtCl6 was 1:1, the obtained AuPt bimetallic nanoparticles-graphene nanocomposite (denoted as Au1Pt1NPs-GR) possessed the highest electrocatalytic activity toward dopamine (DA). As such, Au1Pt1NPs-GR nanocomposites were used to detect DA in the presence of ascorbic acid (AA) and uric acid (UA) using the differential pulse voltammetry (DPV) technique and on the modified electrode, there were three separate DPV oxidation peaks with the peak potential separations of 177 mV, 130 mV and 307 mV for DA and AA, DA and UA, AA and UA, respectively. The linear range of the constructed DA sensor was from 1.6 μM to 39.7 μM with a detection limit of 0.1 μM (S/N = 3). The obtained DA sensor with good stability, high reproducibility and excellent selectivity made it possible to detect DA in human urine samples.

Determination of fluvoxamine maleate in human urine and human serum using alkaline KMnO4 -rhodamine B chemiluminescence.

PubMed

Yang, Dongqin; He, Yanyan; Chen, Funan

2017-09-01

The flow-injection chemiluminescence (FI-CL) behavior of a gold nanocluster (Au NC)-enhanced rhodamine B-KMnO 4 system was studied under alkaline conditions for the first time. In the present study, the as-prepared bovine serum albumin-stabilized Au NCs showed excellent stability and reproducibility. The addition of trace levels of fluvoxamine maleate (Flu) led to an obvious decline in CL intensity in the rhodamine B-KMnO 4 -Au NCs system, which could be used for quantitative detection of Flu. Under optimized conditions, the proposed CL system exhibited a favorable analytical performance for Flu determination in the range 2 to 100 μg ml -1 . The detection limit for Flu measurement was 0.021 μg ml -1 . Moreover, this newly developed system revealed outstanding selectivity for Flu detection when compared with a multitude of other species, such as the usual ions, uric acid and a section of hydroxy compounds. Additionally, CL spectra, UV-visible spectroscopes and fluorescence spectra were measured in order to determine the possible reaction mechanism. This approach could be used to detect Flu in human urine and human serum samples with the desired recoveries and could have promising application under physiological conditions. Copyright © 2017 John Wiley & Sons, Ltd.

Red-emitting fluorescent probe for detecting hypochlorite acid in vitro and in vivo.

PubMed

Chen, Hong; Sun, Tao; Qiao, Xiao-Guang; Tang, Qian-Oian; Zhao, Shan-Chao; Zhou, Zhan

2018-06-12

Due to the importance of hypochlorous acid (HClO) in biological and industrial, development of fluorescent probes for HClO has been an active research area. Here, a new red-emitting ratiometric fluorescent probe (P) was synthesized and well defined characterization via NMR, HR-MS, and fluorescence spectrum, which serves as a selective and sensitive probe for ClO - group. The probe showed a ratiometric fluorescent response to hypochlorite at the emission intensities ratio (I 480 /I 612 ) increasing from 0.28 to 27.46. The emission intensities ratio (I 480 /I 612 ) was linearly enhanced (I 480 /I 612  = 0.064 X + 0.096) with the ClO - concentration range from 1 to 30 μM. The detection limitation for ClO - in aqueous solution is 0.47 μM. Moreover, this biocompatible red-emitting ratiometric fluorescent probe was utilized to the fluorescence imaging of ClO - in living cells and Zebrafish. Copyright © 2018. Published by Elsevier B.V.

Uptake of hexanitrohexaazaisowurtzitane (CL-20) by the earthworm Eisenia fetida through dermal contact.

PubMed

Gong, Ping; Escalon, B Lynn; Hayes, Charolett A; Perkins, Edward J

2008-02-01

The explosive compound hexanitrohexaazaisowurtzitane (CL-20) has been shown to cause both lethal and sublethal (reproductive and neurotoxic) effects in exposed oligochaetes. However, whether worms take up CL-20 and how much CL-20 enters worm bodies leading to toxicity (e.g., lethality) remain to be determined. In the present study, we used high performance liquid chromatography (HPLC) and radiolabeled tracer methods to investigate the CL-20 uptake in the whole worm body after contact exposures. Worms (Eisenia fetida) were exposed to filter paper spiked with non-radioactive or [U-(14)C]-labeled CL-20 for 1-3 d. The radiolabeled tracer method allowed us to detect the parent compound and transformation products in worms exposed to as low as 0.04 microg CL-20 cm(-2) of filter paper. The HPLC method without radiolabeled tracer was far less sensitive with a detection limit of 2.17 microg CL-20 cm(-2). Using the radiolabeled tracer, we were able to demonstrate that the worm body concentration linearly correlated to the filter paper concentration < or =0.34 microg cm(-2) (r=0.94) if no breakdown products are assumed. At higher concentrations, the body concentration increased slowly and saturated at around 11 microg g(-1) dry mass resulting in an estimated lethal critical body burden of 10-15 microg CL-20 g(-1) dry mass. These findings demonstrate that CL-20 or potential transformation products are taken into the earthworm body through dermal contact. This information should prove valuable in assessing the bioaccumulation potential and ecological risks of CL-20.

Pyrophosphate as substrate for alkaline phosphatase activity: A convenient flow-injection chemiluminescence assay.

PubMed

Zhang, Qingfeng; Zhang, Cuiyun; Yang, Meiding; Yu, Donghong; Yu, Cong

2017-11-01

A sensitive and convenient flow-injection chemiluminescence (FI-CL) turn-on assay for alkaline phosphatase (ALP) activity without any label and synthesis is developed. Cu 2+ can catalyze the luminol-H 2 O 2 CL reaction. Pyrophosphate (PPi) can chelate Cu 2+ and therefore the Cu 2+ -mediated luminol-H 2 O 2 CL reaction is inhibited. The addition of ALP can catalyze the hydrolysis of PPi into phosphate ions, Cu 2+ is released and the chemiluminescence recovers. A detection limit of 1 mU/mL ALP is obtained. Copyright © 2017 John Wiley & Sons, Ltd.

Flow-injection chemiluminescence method to detect a β2 adrenergic agonist.

PubMed

Zhang, Guangbin; Tang, Yuhai; Shang, Jian; Wang, Zhongcheng; Yu, Hua; Du, Wei; Fu, Qiang

2015-02-01

A new method for the detection of β2 adrenergic agonists was developed based on the chemiluminescence (CL) reaction of β2 adrenergic agonist with potassium ferricyanide-luminol CL. The effect of β2 adrenergic agonists including isoprenaline hydrochloride, salbutamol sulfate, terbutaline sulfate and ractopamine on the CL intensity of potassium ferricyanide-luminol was discovered. Detection of the β2 adrenergic agonist was carried out in a flow system. Using uniform design experimentation, the influence factors of CL were optimized. The optimal experimental conditions were 1 mmol/L of potassium ferricyanide, 10 µmol/L of luminol, 1.2 mmol/L of sodium hydroxide, a flow speed of 2.6 mL/min and a distance of 1.2 cm from 'Y2 ' to the flow cell. The linear ranges and limit of detection were 10-100 and 5 ng/mL for isoprenaline hydrochloride, 20-100 and 5 ng/mL for salbutamol sulfate, 8-200 and 1 ng/mL for terbutaline sulfate, 20-100 and 4 ng/mL for ractopamine, respectively. The proposed method allowed 200 injections/h with excellent repeatability and precision. It was successfully applied to the determination of three β2 adrenergic agonists in commercial pharmaceutical formulations with recoveries in the range of 96.8-98.5%. The possible CL reaction mechanism of potassium ferricyanide-luminol-β2 adrenergic agonist was discussed from the UV/vis spectra. Copyright © 2014 John Wiley & Sons, Ltd.

Development of a new colorimetric assay for detection of bisphenol-A in aqueous media using green synthesized silver chloride nanoparticles: experimental and theoretical study.

PubMed

Khalililaghab, Shiva; Momeni, Safieh; Farrokhnia, Maryam; Nabipour, Iraj; Karimi, Sadegh

2017-04-01

In the present study, a cost-effective, green and simple synthesis method was applied for preparation of stable silver chloride nanoparticles (AgCl-NPs). The method was done by forming AgCl-NPs from Ag + ions using aqueous extract of brown algae (Sargassum boveanum) obtained from the Persian Gulf Sea. This extract served as capping agent during the formation of AgCl-NPs. Creation of AgCl-NPs was confirmed by UV-visible spectroscopy, powder X-ray diffraction, energy-dispersive X-ray spectroscopy, and high-resolution transmission electron microscopy, while the morphology and size analyses were characterized using high-resolution transmission electron microscopy and dynamic light scattering. After optimization of some experimental conditions, particularly pH, a simple and facile system was developed for the naked-eye detection of bisphenol-A. Moreover, a theoretical study of AgCl interaction with bisphenol-A was performed at the density functional level of theory in both gas and solvent phases. Theoretical results showed that electrostatic and van der Waal interactions play important roles in complexation of bisphenol-A with AgCl-NPs, which can lead to aggregation of the as-prepared AgCl-NPs and results in color change from specific yellow to dark purple, where a new aggregation band induced at 542 nm appears. The absorbance at 542 nm was found to be linearly dependent on the bisphenol-A concentration in the range of 1 × 10 -6 -1 × 10 -4  M, with limit of detection of 45 nM. In conclusion, obtained results from the present study can open up an innovative application of the green synthesis of AgCl-NPs using brown algae extract as colorimetric sensors.

Determination of organic peroxides by liquid chromatography with on-line post-column ultraviolet irradiation and peroxyoxalate chemiluminescence detection.

PubMed

Wada, Mitsuhiro; Inoue, Keiyu; Thara, Ayuko; Kishikawa, Naoya; Nakashima, Kenichiro; Kuroda, Naotaka

2003-02-14

A HPLC method was developed for the simultaneous determination of organic peroxides and hydrogen peroxide with peroxyoxalate chemiluminescence (PO-CL) detection following on-line UV irradiation. Organic peroxides [i.e., benzoyl peroxide (BP), tert.-butyl hydroperoxide (BHP), tert.-butyl perbenzoate (BPB), cumene hydroperoxide (CHP)] were UV irradiated (254 nm, 15 W) to generate hydrogen peroxide, which was determined by PO-CL detection. The conditions for UV irradiation and PO-CL detection were optimized by a flow injection analysis (FIA) system. Generation of hydrogen peroxide from peroxides with on-line UV irradiation also was confirmed by the FIA system by incorporating an enzyme column reactor immobilized with catalase. The separation of four organic peroxides and hydrogen peroxide by HPLC was accomplished isocratically on an ODS column within 30 min. The detection limits (signal-to-noise ratio=3) were 1.1 microM for hydrogen peroxide, 6.8 microM for BP, 31.3 microM for BHP, 7.5 microM for BPB and 1.3 microM for CHP. The proposed method was applied to the determination of BP in wheat flour.

Limit on neutrinoless ββ decay of 136Xe from the first phase of KamLAND-Zen and comparison with the positive claim in 76Ge.

PubMed

Gando, A; Gando, Y; Hanakago, H; Ikeda, H; Inoue, K; Ishidoshiro, K; Kato, R; Koga, M; Matsuda, S; Mitsui, T; Motoki, D; Nakada, T; Nakamura, K; Obata, A; Oki, A; Ono, Y; Otani, M; Shimizu, I; Shirai, J; Suzuki, A; Takemoto, Y; Tamae, K; Ueshima, K; Watanabe, H; Xu, B D; Yamada, S; Yoshida, H; Kozlov, A; Yoshida, S; Banks, T I; Freedman, S J; Fujikawa, B K; Han, K; O'Donnell, T; Berger, B E; Efremenko, Y; Karwowski, H J; Markoff, D M; Tornow, W; Detwiler, J A; Enomoto, S; Decowski, M P

2013-02-08

We present results from the first phase of the KamLAND-Zen double-beta decay experiment, corresponding to an exposure of 89.5 kg yr of (136)Xe. We obtain a lower limit for the neutrinoless double-beta decay half-life of T(1/2)(0ν)>1.9×10(25) yr at 90% C.L. The combined results from KamLAND-Zen and EXO-200 give T(1/2)(0ν)>3.4×10(25) yr at 90% C.L., which corresponds to a Majorana neutrino mass limit of <(120-250) meV based on a representative range of available matrix element calculations. Using those calculations, this result excludes the Majorana neutrino mass range expected from the neutrinoless double-beta decay detection claim in (76)Ge, reported by a part of the Heidelberg-Moscow Collaboration, at more than 97.5% C.L.

A novel chemiluminescence system with diperiodatonickelate (IV) for the determination of adrenaline

NASA Astrophysics Data System (ADS)

Yang, Chunyan; Chen, Fubin; Chang, Ziqiang; Sun, Yonghua; Zhang, Zhujun

2014-03-01

A novel chemiluminescence (CL) system with diperiodatonickelate (IV) (DPN) was developed for the determination of adrenaline for the first time. The possible CL emission mechanism was briefly discussed by comparing the fluorescence emission spectra with CL spectra. Under the optimum conditions, the relative CL intensity was linear over the concentration of AD ranging from 1.0 × 10-7 to 1.0 × 10-5 g mL-1 with a detection limit of 4.0 × 10-8 g mL-1 (3σ). And the relative standard deviation was 3.7% for 2.0 × 10-6 g mL-1 AD (n = 11). The developed method has been successfully applied to the determination of AD in pharmaceutical preparations.

Synthesis and Evaluation of Chlorinated Substrate Analogues for Farnesyl Diphosphate Synthase

PubMed Central

Heaps, Nicole A.; Poulter, C. Dale

2011-01-01

Substrate analogues for isopentenyl diphosphate (IPP) and dimethylallyl diphosphate (DMAPP), where the C3 methyl groups were replaced by chlorine, were synthesized and evaluated as substrates for avian farnesyl diphosphate synthase (FPPase). The IPP analogue (3-ClIPP) was a co-substrate when incubated with dimethylallyl diphosphate (DMAPP) or geranyl diphosphate (GPP) to give the corresponding chlorinated analogues of geranyl diphosphate (3-ClGPP) and farnesyl diphosphate (3-ClFPP), respectively. No products were detected in incubations of 3-ClIPP with 3-ClDMAPP. Incubation of IPP with 3-ClDMAPP gave 11-ClFPP as the sole product. Values of KM3-ClIPP (with DMAPP) and KM3-ClDMAPP (with IPP) were similar to those for IPP and DMAPP, however values of kcat for both analogues were substantially lower. These results are consistent with a dissociative electrophilic alkylation mechanism where the rate-limiting step changes from heterolytic cleavage of the carbon-oxygen bond in the allylic substrate to alkylation of the double bond of the homoallylic substrate. PMID:21344952

Long-term chemiluminescence signal is produced in the course of luminol oxidation catalyzed by enhancer-independent peroxidase purified from Jatropha curcas leaves.

PubMed

Duan, Peipei; Cai, Feng; Luo, Yongting; Chen, Yangxi; Zou, Shujuan

2015-09-01

Isoenzyme c of horseradish peroxidase (HRP-C) is widely used in enzyme immunoassay combined with chemiluminescence (CL) detection. For this application, HRP-C activity measurement is usually based on luminol oxidation in the presence of hydrogen peroxide (H2O2). However, this catalysis reaction was enhancer dependent. In this study, we demonstrated that Jatropha curcas peroxidase (JcGP1) showed high efficiency in catalyzing luminol oxidation in the presence of H2O2. Compared with HRP-C, the JcGP1-induced reaction was enhancer independent, which made the enzyme-linked immunosorbent assay (ELISA) simpler. In addition, the JcGP1 catalyzed reaction showed a long-term stable CL signal. We optimized the conditions for JcGP1 catalysis and determined the favorable conditions as follows: 50 mM Tris buffer (pH 8.2) containing 10 mM H2 O2, 14 mM luminol and 0.75 M NaCl. The optimum catalysis temperature was 30°C. The detection limit of JcGP1 under optimum condition was 0.2 pM. Long-term stable CL signal combined with enhancer-independent property indicated that JcGP1 might be a valuable candidate peroxidase for clinical diagnosis and enzyme immunoassay with CL detection. Copyright © 2014 John Wiley & Sons, Ltd.

Application of silver nanoparticles to the chemiluminescence determination of cefditoren pivoxil using the luminol-ferricyanide system.

PubMed

Alarfaj, Nawal A; Aly, Fatma A; El-Tohamy, Maha F

2015-02-01

A new simple, accurate and sensitive sequential injection analysis chemiluminescence (CL) detection method for the determination of cefditoren pivoxil (CTP) has been developed. The developed method was based on the enhancement effect of silver nanoparticles on the CL signal arising from a luminol-potassium ferricyanide reaction in the presence of CTP. The optimum conditions relevant to the effect of luminol, potassium ferricyanide and silver nanoparticle concentrations were investigated. The proposed method showed linear relationships between relative CL intensity and the investigated drug concentration at the range 0.001-5000 ng/mL, (r = 0.9998, n = 12) with a detection limit of 0.5 pg/mL and quantification limit of 0.001 ng/mL. The relative standard deviation was 1.6%. The proposed method was employed for the determination of CTP in bulk drug, in its pharmaceutical dosage forms and biological fluids such as human serum and urine. The interference of some common additive compounds such as glucose, lactose, starch, talc and magnesium stearate was investigated. In addition, the interference of some related cephalosporins was tested. No interference was recorded. The obtained sequential injection analysis-CL results were statistically compared with those from a reported method and did not show any significant differences. Copyright © 2014 John Wiley & Sons, Ltd.

Simplex optimization of the variables influencing the determination of pefloxacin by time-resolved chemiluminescence

NASA Astrophysics Data System (ADS)

Murillo Pulgarín, José A.; Alañón Molina, Aurelia; Jiménez García, Elisa

2018-03-01

A new chemiluminescence (CL) detection system combined with flow injection analysis (FIA) for the determination of Pefloxacin is proposed. The determination is based on an energy transfer from Pefloxacin to terbium (III). The metal ion enhances the weak CL signal produced by the KMnO4/H2SO3/Pefloxacin system. A modified simplex method was used to optimize chemical and instrumental variables. The influence of the interaction of the permanganate, Tb (III), sodium sulphite and sulphuric acid concentrations, flow rate and injected sample volume was thoroughly investigated by using a modified simplex optimization procedure. The results revealed a strong direct relationship between flow rate and CL intensity throughout the studied range that was confirmed by a gamma test. The response factor for the CL emission intensity was used to assess performance in order to identify the optimum conditions for maximization of the response. Under such conditions, the CL response was proportional to the Pefloxacin concentration over a wide range. The detection limit as calculated according to Clayton's criterion 13.7 μg L- 1. The analyte was successfully determined in milk samples with an average recovery of 100.6 ± 9.8%.

Sensitivity of chloride efflux vs. transepithelial measurements in mixed CF and normal airway epithelial cell populations.

PubMed

Illek, Beate; Lei, Dachuan; Fischer, Horst; Gruenert, Dieter C

2010-01-01

While the Cl(-) efflux assays are relatively straightforward, their ability to assess the efficacy of phenotypic correction in cystic fibrosis (CF) tissue or cells may be limited. Accurate assessment of therapeutic efficacy, i.e., correlating wild type CF transmembrane conductance regulator (CFTR) levels with phenotypic correction in tissue or individual cells, requires a sensitive assay. Radioactive chloride ((36)Cl) efflux was compared to Ussing chamber analysis for measuring cAMP-dependent Cl(-) transport in mixtures of human normal (16HBE14o-) and cystic fibrosis (CF) (CFTE29o- or CFBE41o-, respectively) airway epithelial cells. Cell mixtures with decreasing amounts of 16HBE14o- cells were evaluated. Efflux and Ussing chamber studies on mixed populations of normal and CF airway epithelial cells showed that, as the number of CF cells within the population was progressively increased, the cAMP-dependent Cl(-) decreased. The (36)Cl efflux assay was effective for measuring Cl(-) transport when ≥ 25% of the cells were normal. If < 25% of the cells were phenotypically wild-type (wt), the (36)Cl efflux assay was no longer reliable. Polarized CFBE41o- cells, also homozygous for the ΔF508 mutation, were used in the Ussing chamber studies. Ussing analysis detected cAMP-dependent Cl(-) currents in mixtures with ≥1% wild-type cells indicating that Ussing analysis is more sensitive than (36)Cl efflux analysis for detection of functional CFTR. Assessment of CFTR function by Ussing analysis is more sensitive than (36)Cl efflux analysis. Ussing analysis indicates that cell mixtures containing 10% 16HBE14o- cells showed 40-50% of normal cAMP-dependent Cl(-) transport that drops off exponentially between 10-1% wild-type cells. Copyright © 2010 S. Karger AG, Basel.

Determination of estradiol valerate in pharmaceutical preparations and human serum by flow injection chemiluminescence.

PubMed

Liu, Wenwen; Xie, Liangxiao; Liu, Hongshuang; Xu, Shichao; Hu, Bingcheng; Cao, Wei

2013-01-01

A novel method for the detection of trace estradiol valerate (EV) in pharmaceutical preparations and human serum was developed by inhibition of luminol chemiluminescence (CL) by estradiol valerate on the zinc deuteroporphyrin (ZnDP)-enhanced luminol-K3 Fe(CN)6 chemiluminescence system. Under optimized experimental conditions, CL intensity and concentration of estradiol valerate had a good linear relationship in the ranges of 8.0 × 10(-8) to 1.0 × 10(-5) g/mL. Detection limit (3σ) was estimated to be 3.5 × 10(-8) g/mL. The proposed method was applied successfully for the determination of estradiol valerate in pharmaceutical preparations and human serum and recoveries were 97.0-105.0% and 95.5-106.0%, respectively. The possible mechanism of the CL system is discussed. Copyright © 2012 John Wiley & Sons, Ltd.

Measurement of hydroxyl radical production in ultrasonic aqueous solutions by a novel chemiluminescence method.

PubMed

Hu, Yufei; Zhang, Zhujun; Yang, Chunyan

2008-07-01

Measurement methods for ultrasonic fields are important for reasons of safety. The investigation of an ultrasonic field can be performed by detecting the yield of hydroxyl radicals resulting from ultrasonic cavitations. In this paper, a novel method is introduced for detecting hydroxyl radicals by a chemiluminescence (CL) reaction of luminol-hydrogen peroxide (H2O2)-K5[Cu(HIO6)2](DPC). The yield of hydroxyl radicals is calculated directly by the relative CL intensity according to the corresponding concentration of H2O2. This proposed CL method makes it possible to perform an in-line and real-time assay of hydroxyl radicals in an ultrasonic aqueous solution. With flow injection (FI) technology, this novel CL reaction is sensitive enough to detect ultra trace amounts of H2O2 with a limit of detection (3sigma) of 4.1 x 10(-11) mol L(-1). The influences of ultrasonic output power and ultrasonic treatment time on the yield of hydroxyl radicals by an ultrasound generator were also studied. The results indicate that the amount of hydroxyl radicals increases with the increase of ultrasonic output power (< or = 15 W mL(-1)). There is a linear relationship between the time of ultrasonic treatment and the yield of H2O2. The ultrasonic field of an ultrasonic cleaning baths has been measured by calculating the yield of hydroxyl radicals.

Universal chemiluminescence flow-through device based on directed self-assembly of solid-state organic chromophores on layered double hydroxide matrix.

PubMed

Wang, Zhihua; Teng, Xu; Lu, Chao

2013-02-19

In this work, a universal chemiluminescence (CL) flow-through device suitable for various CL resonance energy transfer (CRET) systems has been successfully fabricated. Highly efficient CRET in solid-state photoactive organic molecules can be achieved by assembling them on the surface of layered double hydroxides (LDHs). We attribute these observations to the suppression of the intermolecular π-π stacking interactions among aromatic rings and the improvement of molecular orientation and planarity in the LDH matrix, enabling a remarkable increase in fluorescence lifetime and quantum yield of organic molecules. Under optimal conditions, using peroxynitrous acid-fluorescein dianion (FLUD) as a model CRET system, trace FLUD (10 μM) was assembled on the surface of LDHs. Peroxynitrous acid/nitrite could be assayed in the range of 1.0-500 μM, and the detection limit for peroxynitrous acid/nitrite (S/N = 3) was 0.6 μM. This CL flow-through device exhibited operational stability, high reproducibility, and long lifetime. While LDHs were immobilized in a flow-through device in the absence of FLUD, the detection limit for peroxynitrous acid/nitrite was 100 μM. On the other hand, FLUD at the same concentration can not enhance the CL intensity of peroxynitrous acid system. This fabricated CL flow-through column has been successfully applied to determine nitrite in sausage samples with recoveries of 98-102%. These satisfactory results demonstrated that our studies pave a novel way toward flow-through column-based CRET using solid-state organic molecules as acceptors for signal amplification.

Turn-off-on chemiluminescence determination of cyanide.

PubMed

Han, Suqin; Wang, Jianbo; Jia, Shize

2015-02-01

A flow injection chemiluminescence (FI-CL) method was developed for the determination of cyanide (CN(-) ) based on the recovered CL signal by Cu(2+) inhibiting a glutathione (GSH)-capped CdTe quantum dot (QD) and hydrogen peroxide system. In an alkaline medium, strong CL signals were observed from the reaction of CdTe QDs and H2O2 , and addition of Cu(2+) could cause significant CL inhibition of the CdTe QDs-H2O2 system. In the presence of CN(-) , Cu(2+) can be removed from the surface of CdTe QDs via the formation of particularly stable [Cu(CN)n ]((n-1)-) species, and the CL signal of the CdTe QDs-H2O2 system was efficiently recovered. Thus, the CL signals of CdTe QDs-H2O2 system were turned off and turned on by the addition of Cu(2+) and CN(-) , respectively. Further, the results showed that among the tested ions, only CN(-) could recover the CL signal, which suggested that the CdTe QDs-H2O2 -Cu(2+) CL system had highly selectivity for CN(-) . Under optimum conditions, the CL intensity and the concentration of CN(-) show a good linear relationship in the range 0.0-650.0 ng/mL (R(2)  = 0.9996). The limit of detection for CN(-) was 6.0 ng/mL (3σ). This method has been applied to detect CN(-) in river water and industrial wastewater with satisfactory results. Copyright © 2014 John Wiley & Sons, Ltd.

An easy prepared dual-channel chemosensor for selective and instant detection of fluoride based on double Schiff-base

NASA Astrophysics Data System (ADS)

Leng, Yan-Li; Zhang, Jian-Hui; Li, Qiao; Zhang, You-Ming; Lin, Qi; Yao, Hong; Wei, Tai-Bao

2016-10-01

A colorimetric and fluorescent dual-channel fluoride chemosensor N,N‧-bis (4-diethylaminosalicylidene) hydrazine (sensor S) bearing two imine groups has been designed and synthesized. This structurally simple probe displays rapid response and high selectivity for fluoride over other common anions (Cl-, Br-, I-, AcO-, H2PO4-, HSO4-, ClO4-, CN- and SCN-) in a highly polar aqueous DMSO solution. Mechanism studies suggested that the sensor firstly combined with F- through hydrogen bonds and then experienced the deprotonation process at higher concentrations of F- anion to the two Ar-OH groups. The detection limit was 5.78 × 10- 7 M of F-, which points to the high detection sensitivity. Test strips based on sensor S were fabricated, which could act as a convenient and efficient F- test kit to detect F- for ;in-the-field; measurement.

Demonstration and Validation of a Portable Raman Sensor for In-Situ Detection and Monitoring of Perchlorate (ClO 4 -)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hatzinger, Paul B.; Eres, Gyula; Gu, Baohua

Costs for environmental analysis and monitoring are increasing at a rapid rate and represent a significant percentage of the total and future remedial expenses at many U.S. Department of Defense (DoD) contaminated sites. It has been reported that about 30 to 40% of the remediation budget is usually spent on long-term monitoring (LTM), of which a large percentage represents laboratory analytical costs. Energetics such as perchlorate (ClO 4 -) are among the most frequently detected contaminants in groundwater and surface water at or near military installations due to their persistence and mobility. Currently, the standard protocol entails collecting samples inmore » the field, packaging them, and shipping them overnight to a designated laboratory for analysis. This process requires significant sample preparation and handling, and analytical results may not be available for several days to weeks. In this project, we developed and demonstrated a portable Raman sensor based on surface enhanced Raman scattering (SERS) technology to detect ClO 4 - in contaminated water. We summarize major accomplishments as follows: • A SERS sensor based on elevated gold (Au) nano-ellipse dimer architectures was designed and developed for ClO 4 - with a detection limit of ~10 -6 M (or 100 μg/L); The performance of these sensors was evaluated and optimized through variation of their geometric characteristics (i.e., dimer aspect ratio, dimer separation, etc.). • Large-scale commercial production of SERS substrate sensors via nanoimprinting by Nanova Inc. and Nanoimprint lithography (NIL) technology was successfully demonstrated. This is a substantial step forward toward the commercialization of the SERS sensors and may potentially lead to significantly reduced fabrication costs of SERS substrates. • Commercially produced SERS sensors were demonstrated to detect ClO 4 - at levels above 10 -6 M using a portable Raman analyzer. The performance of the commercial SERS sensors for ClO 4 - detection in the presence and absence of interferences was determined for a series of standard solutions. Sulfate (SO 4 2-) was found to exhibit the greatest interference for the anions tested, which included Cl-, NO 3 -, and SO 4 2-. • Field demonstration of the portable Raman sensor with commercially produced SERS substrates was completed at two Department of Defense (DoD) sites; twice at the Indian Head Naval Surface Warfare Center, Indian Head, MD, and once at Redstone Arsenal, Huntsville, AL. Multiple wells were sampled at both DoD sites, where a standard addition method was employed using the sensor to determine the ClO 4 -4 - and possibly other energetics that are both important for environmental monitoring and of interest for national security. However, we point out that SERS technology is also prone to interferences due to its sensitivity and responses to other ionic species, such as NO 3 -, SO 4 2-, and dissolved organics or co-contaminants present in the groundwater, which could potentially mask the SERS signal of the target analyte (i.e., ClO 4 -). As such, SERS analysis was subject to significant variations (e.g., ±20% or more), and its detection limit for ClO 4 --8 M) and was substantially higher than what we anticipated from laboratory studies. However, despite these complications, the portable Raman sensor developed in this project could be used as a rapid screening tool for ClO 4 - at concentrations above 10 -6 M. Future studies are warranted to further develop the technology and to optimize its performance, and eventually to bring the technology to the market. With additional development and demonstration, the sensor has the potential to reduce analytical costs by eliminating shipping and typical costs associated with laboratory analysis. A cost savings of 30–45% may be realized during a typical sampling event and, more importantly, the technology could allow rapid turn-around of information to decision makers for site characterization and remediation.« less

Sodium hypochlorite oxidation of petroleum aliphatic contaminants in calcareous soils.

PubMed

Picard, François; Chaouki, Jamal

2016-02-01

This research project investigated the sodium hypochlorite (NaClO) oxidation of aliphatic petroleum contaminants (C10-C50) in a calcareous soil (average 5473 ppm C10-C50, 15 wt% Ca), which had been excavated from a contaminated industrial site. The decontamination objective was to lower the C10-C50 concentration to 700 ppm. CO2 acidity was used in the project to boost the NaClO oxidation yield and seems to have played a role in desorbing the natural organic matter. The experimental conditions were a 2- to 16-h reaction time, at room temperature, with a 1 to 12.5 wt% NaClO oxidative solution and a fixed 2:1 solution-to-soil ratio. With a 3 wt% NaClO solution and with a CO2 overhead, the NaClO dosage requirement was maintained below 60 g NaClO/g of oxidized C10-C50 over the entire decontamination range. The strong chlorine smell remaining after the reaction was completed suggests that part of the NaClO requirement can be recycled. Except traces of chloroform, there were no regulation-listed organochloride contaminants detected on either the treated soil samples or leachates and the total count of chlorinated compounds in treated soil samples was below the detection limit of 250 mg/kg. The NaClO oxidation mechanism on aliphatic substrates might be triggered by transition metals, such as manganese, but no attempt has been made to investigate the oxidation mechanism. Further investigations would include a constant-fed NaClO system and other techniques to lower the required NaClO dosage. Copyright © 2015 Elsevier Ltd. All rights reserved.

Application of Highly Purified Electrolyzed Chlorine Dioxide for Tilapia Fillet Disinfection

PubMed Central

Yu, Chen-Hsing; Huang, Tzou-Chi; Chung, Chao-Chin; Huang, Hao-Hsun

2014-01-01

This research aimed to develop an electrolysis method to generate high-concentration chlorine dioxide (ClO2) for tilapia fillet disinfection. The designed generator produced up to 3500 ppm of ClO2 at up to 99% purity. Tilapia fillets were soaked in a 400 ppm ClO2 solution for 5, 10, and 25 min. Results show that total plate counts of tilapia, respectively, decreased by 5.72 to 3.23, 2.10, and 1.09 log CFU/g. In addition, a 200 ppm ClO2 solution eliminated coliform bacteria and Escherichia coli in 5 min with shaking treatment. Furthermore, ClO2 and trihalomethanes (THMs) residuals on tilapia fillets were analyzed by GC/MS and were nondetectable (GC-MS detection limit was 0.12 ppb). The results conform to Taiwan's environmental protection regulations and act governing food sanitation. PMID:24696651

CdS nanoparticles-enhanced chemiluminescence and determination of baicalin in pharmaceutical preparations.

PubMed

Chen, Xiaolan; Tan, Xinmei; Wang, Jianxiu

2013-01-01

CdS nanoparticles (CdS NPs) of different sizes were synthesized by the citrate reduction method. It was found that CdS NPs could enhance the chemiluminescence (CL) of the luminol-potassium ferricyanide system and baicalin could inhibit CdS NPs-enhanced luminol-potassium ferricyanide CL signals in alkaline solution. Based on this inhibition, a flow-injection CL method was established for determination of baicalin in pharmaceutical preparations and human urine samples. Under optimized conditions, the linear range for determination of baicalin was 5.0 x 10(-6) to 1.0 x 10(-3) g/L. The detection limit at a signal-to-noise ratio of 3 was 1.7 x 10(-6) g/L. CL spectra, UV-visible spectra and transmission electron microscopy (TEM) were used to investigate the CL mechanism. The method described is simple, selective and obviates the need of extensive sample pretreatment. Copyright © 2012 John Wiley & Sons, Ltd.

Determination of berberine in pharmaceutical preparations using acidic hydrogen peroxide-nitrite chemiluminescence system.

PubMed

Liang, Yao-Dong; Yu, Chun-Xia

2013-03-01

A stronger chemiluminescence (CL) was observed when hydrogen peroxide was mixed with nitrite and berberine in sulfuric acid solution. The stronger CL originated from peroxidation of berberine by peroxynitrous acid that was synthesized online by the mixing of acidic hydrogen peroxide solution with nitrite solution in a flow system. The emitting species was excited state oxyberberine, a peroxidized product of berberine. Based on the stronger CL, a flow injection CL method for the determination of berberine was proposed. Under optimum experimental conditions, the stronger CL intensity was linearly related to the concentration of berberine over the range of 2.0 × 10(-7) -2.0 × 10(-5) mol L(-1) . The limit of detection (s/n = 3) was 6.2 × 10(-8) mol L(-1) . The proposed method has been evaluated by analyzing berberine in pharmaceutical preparations. Copyright © 2011 John Wiley & Sons, Ltd.

Is there any chlorine monoxide in the stratosphere?

NASA Technical Reports Server (NTRS)

Mumma, M. J.; Rogers, J. D.; Kostiuk, T.; Deming, D.; Hillman, J. J.; Zipoy, D.

1983-01-01

A ground-based search for stratospheric 35-ClO was carried out using an infrared heterodyne spectrometer in the solar absorption mode. Lines due to stratospheric HNO3 and tropospheric OCS were detected at about 0.2% absorptance levels, but the expected 0.1% lines of ClO in this same region were not seen. We find that stratospheric ClO is at least a factor of seven less abundant than is indicated by in situ measurements, and we set an upper limit of 2.3x10 to the 13th molecules/sq cm at the 95% confidence level for the integrated vertical column density of ClO. Our results imply that the release of chlorofluorocarbons may be significantly less important for the destruction of stratospheric ozone (O3) than is currently thought.

A chemiluminescence biosensor for the detection of thrombin based on the aptamer composites

NASA Astrophysics Data System (ADS)

Lin, Yanna; Li, Jianbo; Wang, Yanhui; Sun, Yuanling; Ding, Chaofan; Sun, Weiyan; Luo, Chuannan

2018-03-01

An efficient, rapid, simple and ultrasensitive chemiluminescence (CL) approach was proposed for thrombin detection based on the aptamer-thrombin recognition. The aptamer composites were synthesized in this work using graphene oxide (GO) as the backing material. The thrombin was adsorbed on the aptamer composites based on the aptamer-thrombin recognition. Thus, thrombin could be quantified by the difference value of the CL intensity between supernate of the sample and the mixture which composed of thrombin and coexisted substances. The CL intensity exhibits a stable response to thrombin over a concentration range from 2.5 × 10- 10 to 1 × 10- 9 mol·L- 1 with a detection limit as low as 8.3 × 10- 11 mol·L- 1, the relative standard deviation (RSD) was found to be 4.9% for 11 determinations of 1.25 × 10- 9 mol·L- 1 thrombin. Finally, the applicability of the method was verified by applying to serum samples. The recoveries were in the range of 90.3-101.0% with RSD of 2.6-3.2%.

Assay of picogram level isocarbophos residue on tangerines and oranges with luminol-albumin chemiluminescence system.

PubMed

Chen, Donghua; Song, Zhenghua; Lv, Hairu

2012-12-15

A sensitive flow injection-chemiluminescence (FI-CL) method for the determination of isocarbophos (ICP) residue on tangerines and oranges was proposed. It was found that the CL intensity from luminol-albumin CL reaction could be obviously quenched in the presence of ICP and the decrease in CL intensity was proportional to the logarithm of ICP concentrations ranging from 1.0 to 1000 pmol L(-1), giving the limit of detection of 0.3 pmol L(-1) (3σ). The proposed procedure was successfully applied to the determination of ICP residue on tangerines and oranges with recoveries varying from 92.0 to 111.0% and RSDs less than 5.0%. The possible CL mechanism of luminol-albumin-ICP reaction was discussed, and ICP to albumin's binding constant (K(D)=1.00 × 10(6) L mol(-1)) and the number of binding sites (n=1.00) were given by the homemade FI-CL model. Copyright © 2012 Elsevier Ltd. All rights reserved.

In situ observations of midlatitude stratospheric ClO and BrO

NASA Technical Reports Server (NTRS)

Brune, William H.; Anderson, James C.

1986-01-01

A balloon-borne experiment to measure midlatitude stratospheric BrO and ClO concentrations by NO chemical conversion/atomic resonance fluorescence was flown from Palestine, Texas, on May 20 1986. In this first study of BrO, no signal attributable to BrO was detected, and upper limits (2 sigma uncertainty) between 35 and 24 km altitude give BrO mixing ratios less than 15 pptv. Current models predict mixing ratios that are 1.7 times larger. Measurements of ClO were obtained at less than 0.2-km altitude resolution from 41 to 22 km. The smoothly varying altitude profile lies within the range of two-dimensional model calculations.

Stimulus-response mesoporous silica nanoparticle-based chemiluminescence biosensor for cocaine determination.

PubMed

Chen, Zhonghui; Tan, Yue; Xu, Kefeng; Zhang, Lan; Qiu, Bin; Guo, Longhua; Lin, Zhenyu; Chen, Guonan

2016-01-15

Mesoporous silica nanoparticles (MSN) based controlled release system had been coupled with diverse detection technologies to establish biosensors for different targets. Chemiluminescence (CL) system of luminol/H2O2 owns the characters of simplicity, low cost and high sensitivity, but the targets of which are mostly focused on some oxidants or which can participate in a chemical reaction that yields a product with a role in the CL reaction. In this study, chemiluminescent detection technique had been coupled with mesoporous silica-based controlled released system for the first time to develop a sensitive biosensor for the target which does not cause effect to the CL system itself. Cocaine had been chosen a model target, the MSN support was firstly loaded with glucose, then the positively charged MSN interacted with negatively charged oligonucleotides (the aptamer cocaine) to close the mesopores of MSN. At the present of target, cocaine binds with its aptamer with high affinity; the flexible linear aptamer structured will become stems structured through currently well-defined non-Waston-Crick interactions and causes the releasing of entrapped glucose into the solution. With the assistant of glucose oxidase (GOx), the released glucose can react with the dissolved oxgen to produce gluconic acid and H2O2, the latter can enhance the CL of luminol in the NaOH solution. The enhanced CL intensity has a relationship with the cocaine concentration in the range of 5.0-60μM with the detection limit of 1.43μM. The proposed method had been successfully applied to detect cocaine in serum samples with high selectivity. The same strategy can be applied to develop biosensors for different targets. Copyright © 2015 Elsevier B.V. All rights reserved.

Label-free, non-derivatization CRET detection platform for 6-mercaptopurine based on the distance-dependent optical properties of gold nanoparticles.

PubMed

Du, Jianxiu; Wang, Yadi; Zhang, Weimin

2012-07-02

A label-free, non-derivatization chemiluminescence resonance energy transfer (CRET) detection platform has been developed for the detection of the non-fluorescent small molecule 6-mercaptopurine. This CRET process arose from a chemiluminescent (CL) donor-acceptor system in which the reaction of bis(2,4,6-trichlorophenyl)oxalate (TCPO)-H(2)O(2)-fluorescein (maximum emission at 521.6 nm) served as the donor and gold nanoparticles (AuNPs, maximum absorption at 520.0 nm) served as the acceptor. This process caused a significant decrease in the CL signal of the TCPO-H(2)O(2)-fluorescein reaction. The presence of 6-mercaptopurine induced an aggregation of AuNPs with the assistance of Cu(2+) ions through cooperative metal-ligand interactions that was accompanied by a distinct change in color and optical properties. The maximum absorption band of the AuNPs was red-shifted to 721.0 nm and no longer overlapped with the CL spectrum of the reaction; as a result, the CL signal was restored. This CRET system exhibited a wide linear range, from 9.0 nmol L(-1) to 18.0 μmol L(-1), and a low detection limit (0.62 nmol L(-1)) for 6-mercaptopurine. The applicability of the proposed CRET system was evaluated by analysis of 6-mercaptopurine in spiked human plasma samples. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oil-in-Water Emulsion Exhibits Bitterness-Suppressing Effects in a Sensory Threshold Study.

PubMed

Torrico, Damir Dennis; Sae-Eaw, Amporn; Sriwattana, Sujinda; Boeneke, Charles; Prinyawiwatkul, Witoon

2015-06-01

Little is known about how emulsion characteristics affect saltiness/bitterness perception. Sensory detection and recognition thresholds of NaCl, caffeine, and KCl in aqueous solution compared with oil-in-water emulsion systems were evaluated. For emulsions, NaCl, KCl, or caffeine were dissolved in water + emulsifier and mixed with canola oil (20% by weight). Two emulsions were prepared: emulsion 1 (viscosity = 257 cP) and emulsion 2 (viscosity = 59 cP). The forced-choice ascending concentration series method of limits (ASTM E-679-04) was used to determine detection and/or recognition thresholds at 25 °C. Group best estimate threshold (GBET) geometric means were expressed as g/100 mL. Comparing NaCl with KCl, there were no significant differences in detection GBET values for all systems (0.0197 - 0.0354). For saltiness recognition thresholds, KCl GBET values were higher compared with NaCl GBET (0.0822 - 0.1070 compared with 0.0471 - 0.0501). For NaCl and KCl, emulsion 1 and/or emulsion 2 did not significantly affect the saltiness recognition threshold compared with that of the aqueous solution. However, the bitterness recognition thresholds of caffeine and KCl in solution were significantly lower than in the emulsions (0.0242 - 0.0586 compared with 0.0754 - 0.1025). Gender generally had a marginal effect on threshold values. This study showed that, compared with the aqueous solutions, emulsions did not significantly affect the saltiness recognition threshold of NaCl and KCl, but exhibited bitterness-suppressing effects on KCl and/or caffeine. © 2015 Institute of Food Technologists®

Chemiluminescent detection of cell apoptosis enzyme by gold nanoparticle-based resonance energy transfer assay.

PubMed

Huang, Xiangyi; Liang, Yiran; Ruan, Lingao; Ren, Jicun

2014-09-01

We report a new chemiluminescence resonance energy transfer (CRET) technique, using gold nanoparticles (AuNPs) as efficient energy acceptor, for homogeneous measurement of cell apoptosis enzyme with high sensitivity. In the design of the CRET system, we chose the highly sensitive chemiluminescence (CL) reaction between luminol and hydrogen peroxide catalysed by horseradish peroxidase (HRP) because the CL spectrum of luminol (λ max 425 nm) partially overlaps the visible absorption bands of AuNPs. In this system, the peptide substrate (DEVD) of caspase 3 was linked to the AuNP surface by Au-S linkage. HRP was attached to the AuNP surface by means of a bridge formed by the streptavidin-biotin reaction. CRET occurred as a result of formation of AuNP-peptide-biotin-streptavidin-HRP complexes. The CL of luminol was significantly reduced, because of the quenching effect of AuNPs. The quenched CL was recovered after cleavage of DEVD by caspase 3, an enzyme involved in the apoptotic process. Experimental conditions were systematically investigated. Under the optimum conditions the increase of the CL signal was linearly dependent on caspase 3 concentration within the concentration range 25 pmol L(-1) to 800 pmol L(-1) and the detection limit of caspase 3 was as low as 20 pmol L(-1), one order of magnitude lower than for FRET sensors based on graphene oxides. Our method was successfully used to detect drug-induced apoptosis of cells. This approach is expected to be extended to other assays, i.e., using other enzymes, analytes, CL substances, and even other nanoparticles (e.g., quantum dots and graphene).

Congener-specific determination of ultratrace levels of chlorinated and brominated polycyclic aromatic hydrocarbons in atmosphere and industrial stack gas by isotopic dilution gas chromatography/high resolution mass spectrometry method.

PubMed

Jin, Rong; Liu, Guorui; Zheng, Minghui; Fiedler, Heidelore; Jiang, Xiaoxu; Yang, Lili; Wu, Xiaolin; Xu, Yang

2017-08-04

Isotopic dilution gas chromatography combined with high resolution mass spectrometry (GC/HRMS) has overwhelming advantages with respect to the accuracy of congener-specific ultratrace analysis of complex persistent organic pollutants (POPs) in environmental matrices. However, an isotopic dilution GC/HRMS method for analysis of chlorinated and brominated polycyclic aromatic hydrocarbons (Cl-PAHs and Br-PAHs) using 13 C-labelled congeners as internal standards has not been established. In this study, a method for identification and quantification of 38 congeners of Cl-PAHs and Br-PAHs in atmosphere and stack gas samples from waste incinerators was developed using the isotopic dilution GC/HRMS technique. The instrumental detection limits of the GC/HRMS method ranged from 0.2pg to 1.8pg for Cl-PAH congeners, and 0.7pg to 2.7pg for Br-PAH congeners, which were about three orders of magnitude lower than those of the GC/quadrupole MS method. This new method developed was also the first to enable determination of Cl-PAH and Br-PAH homologs comprising congeners with the same molecular skeleton and chlorine or bromine substitution numbers. Among the detected congeners, seven Cl-PAH congeners and thirteen Br-PAH congeners that were abundant in the atmosphere and stack gases released from waste incinerators were firstly detected in real samples and reported using the established isotopic dilution GC/HRMS method. The developed isotopic dilution GC/HRMS is significant and needed for better studying the environmental behavior and health risk of Cl-PAHs and Br-PAHs. Copyright © 2017 Elsevier B.V. All rights reserved.

Substituted copper phthalocyanine/multiwalled carbon nanotubes hybrid material for Cl{sub 2} sensing application

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharma, Anshul Kumar, E-mail: dramanmahajan@yahoo.co.in; Saini, Rajan, E-mail: dramanmahajan@yahoo.co.in; Singh, Rajinder, E-mail: dramanmahajan@yahoo.co.in

2014-04-24

In this work, hybrid of soluble copper phthalocyanine (CuPcOC{sub 8}) and functionalized multi-walled carbon nanotubes (MWCNTs) has been synthesized. The formation of CuPcOC{sub 8}-MWCNTs hybrid is confirmed by atomic force microscopy, UV-Visible and FTIR spectroscopy. Subsequently, a chemi-resistive sensor is fabricated by drop casting CuPcOC{sub 8}-MWCNTs hybrid onto glass substrate. It has been demonstrated that CuPcOC{sub 8}-MWCNTs hybrid is highly selective towards Cl{sub 2} gas with minimum detection limit of 100 ppb. The response of sensor increases linearly with increase in the concentration of Cl{sub 2} gas. For 2000 ppb of Cl{sub 2}, CuPcOC{sub 8}-MWCNTs hybrid gives a response asmore » large as 53% in 40 seconds.« less

Quantitative determination of aqueous-phase ozone by chemiluminescence using indigo-5,5'-disulfonate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Takeuchi, K.; Ibusuki, T.

1989-03-15

Indigo-5,5'-disulfonate (IDS) was found to be an efficient reagent for the determination of ozone by chemiluminescence (CL); hence it was applied to the continuous measurements of dissolved ozone (O/sub 3/(aq)). The optimum reagent composition was determined as 10 mg L-1 IDS plus 2 mM phosphate (pH 7.2). The CL intensity was proportional to the O/sub 3/(aq) concentration in the range of 0.025-410 ng mL-1. The detection limit was 0.006 ng mL-1, which is 3 orders of magnitude lower than that obtained by spectrophotometry using IDS as reported previously. The reduction of interferences from aldehydes and hydrogen peroxide was attempted. Furthermore,more » the mechanism of the CL was discussed from CL and fluorescence spectra measured.« less

The effect of a solid surface on the segregation and melting of salt hydrates.

PubMed

Zhang, Yu; Anim-Danso, Emmanuel; Dhinojwala, Ali

2014-10-22

Considering the importance of salt and water on earth, the crystallization of salt hydrates next to solid surfaces has important implications in physical and biological sciences. Heterogeneous nucleation is driven by surface interactions, but our understanding of hydrate formation near surfaces is limited. Here, we have studied the hydrate formation of three commonly prevalent salts, MgCl2, CaCl2, and NaCl, next to a sapphire substrate using surface sensitive infrared-visible sum frequency generation (SFG) spectroscopy. SFG spectroscopy can detect the crystallization and melting of salt hydrates at the interface by observing the changes in the intensity and the location of the cocrystallized water hydroxyl peaks (3200-3600 cm(-1)). The results indicate that the surface crystal structures of these three hydrates are similar to those in the bulk. For the NaCl solution, the brine solution is segregated next to the sapphire substrate after the formation of the ice phase. In contrast, the MgCl2 and CaCl2 surface hydrate crystals are interdispersed with nanometer-size ice crystals. The nanosize ice crystals melt at much lower temperatures than bulk ice crystals. For NaCl and MgCl2 solution, the NaCl hydrates prefer to crystallize next to the sapphire substrate instead of the ice crystals and MgCl2 hydrates.

Dissociative recombination of HCl+, H2Cl+, DCl+, and D2Cl+ in a flowing afterglow

NASA Astrophysics Data System (ADS)

Wiens, Justin P.; Miller, Thomas M.; Shuman, Nicholas S.; Viggiano, Albert A.

2016-12-01

Dissociative recombination of electrons with HCl+, H2Cl+, DCl+, and D2Cl+ has been measured under thermal conditions at 300, 400, and 500 K using a flowing afterglow-Langmuir probe apparatus. Measurements for HCl+ and DCl+ employed the variable electron and neutral density attachment mass spectrometry (VENDAMS) method, while those for H2Cl+ and D2Cl+ employed both VENDAMS and the more traditional technique of monitoring electron density as a function of reaction time. At 300 K, HCl+ and H2Cl+ recombine with kDR = 7.7±2.14.5 × 10-8 cm3 s-1 and 2.6 ± 0.8 × 10-7 cm3 s-1, respectively, whereas D2Cl+ is roughly half as fast as H2Cl+ with kDR = 1.1 ± 0.3 × 10-7 cm3 s-1 (2 σ confidence intervals). DCl+ recombines with a rate coefficient below the approximate detection limit of the method (≲5 × 10-8 cm3 s-1) at all temperatures. Relatively slow dissociative recombination rates have been speculated to be responsible for the large HCl+ and H2Cl+ abundances in interstellar clouds compared to current astrochemical models, but our results imply that the discrepancy must originate elsewhere.

A comparative physico-chemical study of chlorapatite and hydroxyapatite: from powders to plasma sprayed thin coatings.

PubMed

Demnati, I; Grossin, D; Combes, C; Parco, M; Braceras, I; Rey, C

2012-10-01

Due to their bioactivity and osteoconductivity, hydroxyapatite (HA) plasma sprayed coatings have been widely developed for orthopedic uses. However, the thermodynamic instability of HA leads frequently to a mixture of phases which limit the functional durability of the coating. This study investigates the plasma spraying of chlorapatite (ClA) powder, known to melt without decomposition, onto pure titanium substrates using a low energy plasma spray system (LEPS). Pure ClA powder was prepared by a solid gas reaction at 950 °C and thermogravimetric analysis showed the good thermal stability of ClA powder in the range 30-1400 °C compared to that of the HA powder. Characterization of ClA coating showed that ClA had a very high crystalline ratio and no other crystalline phase was detected in the coating. HA and ClA coatings composition, microstructure and in vitro bioactivity potential were studied, compared and discussed. In vitro SBF test on HA and ClA coatings revealed the formation of a poorly crystalline apatite on the coating surface suggesting that we could expect a good osteoconductivity especially for the ClA coating prepared by the LEPS system.

An amplified chemiluminescence system based on Si-doped carbon dots for detection of catecholamines.

PubMed

Amjadi, Mohammad; Hallaj, Tooba; Manzoori, Jamshid L; Shahbazsaghir, Tahmineh

2018-08-05

We report on a chemiluminescence (CL) system based on simultaneous enhancing effect of Si-doped carbon dots (Si-CDs) and cetyltrimethylammonium bromide (CTAB) on HCO 3 - -H 2 O 2 reaction . The possible CL mechanism is investigated and discussed. Excited-state Si-CDs was found to be the final emitting species, which are probably produced via electron and hole injection by oxy-radicals. The effect of several other heteroatom-doped CDs and undoped CDs was also investigated and compared with Si-CDs. Furthermore, it was found that catecholamines such as dopamine, adrenaline and noradrenaline remarkably diminish the CL intensity of Si-CD-HCO 3 - -H 2 O 2 -CTAB system. By taking advantage of this fact, a sensitive probe was designed for determination of dopamine, adrenaline and noradrenaline with a limit of detection of 0.07, 0.60 and 0.01 μM, respectively. The method was applied to the determination of catecholamines in human plasma samples. Copyright © 2018 Elsevier B.V. All rights reserved.

N-bromosuccinimide-fluorescein based sensitive flow-injection chemiluminescence determination of phenformin.

PubMed

Wang, Zhouping; Zhang, Zhujun; Fu, Zhifeng; Fang, Luqiu; Zhang, Xiao

2004-02-01

A novel and highly sensitive method for the determination of phenformin over the range of 6 x 10(-9) - 1 x 10(-5) g ml(-1) in pharmaceutical formulations with flow-injection chemiluminescence (CL) detection is proposed. The method is based on the CL produced during the oxidation of N-bromosuccinimide (NBS) in an alkaline medium in the presence of fluorescein as an effective energy transfer agent. The use of cetyltrimethylammonium bromide (CTAB) as a sensitizer enhances the signal magnitude by about 100 times. The detection limit is 2 x 10(-9) g ml(-1) (3sigma) with a relative standard deviation of 2.3% (n = 11) at 1 x 10(-7) g ml(-1) phenformin. Ninety samples can be determined per hour. The method was evaluated by carrying out a recovery study and by the analysis of commercial formulations. The obtained results compared well with those by an official method, and demonstrated good accuracy and precision. The possible CL mechanism of the proposed system was also briefly analyzed.

Identification and Characterization of Natural Sources of Perchlorate

DTIC Science & Technology

2017-01-01

western USA indicating a predominantly natural atmospheric source of ClO4- in all of the lakes. Bomb -pulse 36Cl is largely retained in Lake Superior...from modern (e.g., JYT-1 with 100 percent modern C and post- bomb 3H) to more than 10,000 years (e.g., MW3 with 34 percent modern C and 3H near the...detection limit); however, there is evidence for mixing of old and young water in some cases (MW2 with low 14C and post- bomb 3H) (Table 2.1.4). 22

A flow injection chemiluminescence system for the determination of isoniazid.

PubMed

Huang, Y; Zhang, Z; Zhang, D; Lv, J

2000-10-01

A chemiluminescence (CL) flow system is described for the determination of isoniazid based on its enhancement on the chemiluminescence (CL) emission produced upon mixing a hexacyanoferrate(III) solution with an alkaline luminol solution. The system responds linearly to isoniazid concentration in the range 0-1 mg/L with a detection limit (3sigma) of 0.03 microg/L, relative standard deviation (RSD) of 1.2% for 0.1 mg/L isoniazid (n = 11). The system has been successfully applied to the determination of isoniazid in pharmaceutical preparations.

Real time imaging of live cell ATP leaking or release events by chemiluminescence microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yun

The purpose of this research was to expand the chemiluminescence microscopy applications in live bacterial/mammalian cell imaging and to improve the detection sensitivity for ATP leaking or release events. We first demonstrated that chemiluminescence (CL) imaging can be used to interrogate single bacterial cells. While using a luminometer allows detecting ATP from cell lysate extracted from at least 10 bacterial cells, all previous cell CL detection never reached this sensitivity of single bacteria level. We approached this goal with a different strategy from before: instead of breaking bacterial cell membrane and trying to capture the transiently diluted ATP with themore » firefly luciferase CL assay, we introduced the firefly luciferase enzyme into bacteria using the modern genetic techniques and placed the CL reaction substrate D-luciferin outside the cells. By damaging the cell membrane with various antibacterial drugs including antibiotics such as Penicillins and bacteriophages, the D-luciferin molecules diffused inside the cell and initiated the reaction that produces CL light. As firefly luciferases are large protein molecules which are retained within the cells before the total rupture and intracellular ATP concentration is high at the millmolar level, the CL reaction of firefly luciferase, ATP and D-luciferin can be kept for a relatively long time within the cells acting as a reaction container to generate enough photons for detection by the extremely sensitive intensified charge coupled device (ICCD) camera. The result was inspiring as various single bacterium lysis and leakage events were monitored with 10-s temporal resolution movies. We also found a new way of enhancing diffusion D-luciferin into cells by dehydrating the bacteria. Then we started with this novel single bacterial CL imaging technique, and applied it for quantifying gene expression levels from individual bacterial cells. Previous published result in single cell gene expression quantification mainly used a fluorescence method; CL detection is limited because of the difficulty to introduce enough D-luciferin molecules. Since dehydration could easily cause proper size holes in bacterial cell membranes and facilitate D-luciferin diffusion, we used this method and recorded CL from individual cells each hour after induction. The CL light intensity from each individual cell was integrated and gene expression levels of two strain types were compared. Based on our calculation, the overall sensitivity of our system is already approaching the single enzyme level. The median enzyme number inside a single bacterium from the higher expression strain after 2 hours induction was quantified to be about 550 molecules. Finally we imaged ATP release from astrocyte cells. Upon mechanical stimulation, astrocyte cells respond by increasing intracellular Ca 2+ level and releasing ATP to extracellular spaces as signaling molecules. The ATP release imaged by direct CL imaging using free firefly luciferase and D-luciferin outside cells reflects the transient release as well as rapid ATP diffusion. Therefore ATP release detection at the cell surface is critical to study the ATP release mechanism and signaling propagation pathway. We realized this cell surface localized ATP release imaging detection by immobilizing firefly luciferase to streptavidin beads that attached to the cell surface via streptavidin-biotin interactions. Both intracellular Ca 2+ propagation wave and extracellular ATP propagation wave at the cell surface were recorded with fluorescence and CL respectively. The results imply that at close distances from the stimulation center (<120 μm) extracellular ATP pathway is faster, while at long distances (>120 μm) intracellular Ca 2+ signaling through gap junctions seems more effective.« less

CdTe quantum dots@luminol as signal amplification system for chrysoidine with chemiluminescence-chitosan/graphene oxide-magnetite-molecularly imprinting sensor

NASA Astrophysics Data System (ADS)

Duan, Huimin; Li, Leilei; Wang, Xiaojiao; Wang, Yanhui; Li, Jianbo; Luo, Chuannan

2016-01-01

A sensitive chemiluminescence (CL) sensor based on chemiluminescence resonance energy transfer (CRET) in CdTe quantum dots@luminol (CdTe QDs@luminol) nanomaterials combined with chitosan/graphene oxide-magnetite-molecularly imprinted polymer (Cs/GM-MIP) for sensing chrysoidine was developed. CdTe QDs@luminol was designed to not only amplify the signal of CL but also reduce luminol consumption in the detection of chrysoidine. On the basis of the abundant hydroxy and amino, Cs and graphene oxide were introduced into the GM-MIP to improve the adsorption ability. The adsorption capacities of chrysoidine by both Cs/GM-MIP and non-imprinted polymer (Cs/GM-NIP) were investigated, and the CdTe QDs@luminol and Cs/GM-MIP were characterized by UV-vis, FTIR, SEM and TEM. The proposed sensor can detect chrysoidine within a linear range of 1.0 × 10- 7 - 1.0 × 10- 5 mol/L with a detection limit of 3.2 × 10- 8 mol/L (3δ) due to considerable chemiluminescence signal enhancement of the CdTe quantum dots@luminol detector and the high selectivity of the Cs/GM-MIP system. Under the optimal conditions of CL, the CdTe QDs@luminol-Cs/GM-MIP-CL sensor was used for chrysoidine determination in samples with satisfactory recoveries in the range of 90-107%.

Highly sensitive glucose biosensor based on the effective immobilization of glucose oxidase/carbon-nanotube and gold nanoparticle in nafion film and peroxyoxalate chemiluminescence reaction of a new fluorophore.

PubMed

Zargoosh, Kiomars; Chaichi, Mohammad Javad; Shamsipur, Mojtaba; Hossienkhani, Saman; Asghari, Sakineh; Qandalee, Mohammad

2012-05-15

A novel glucose biosensor based on the chemiluminescence (CL) detection of enzymatically generated H(2)O(2) was constructed by the effective immobilization of glucose oxidase (GOD)/carbon-nanotubes (CNTs)/gold nanoparticles (GNPs) in nafion film on graphite support. The influences of various experimental parameters such as solution pH, the action time of the enzyme, interferents and the concentration of CL reagents were investigated. Carbon nanotubes and gold nanoparticles offer excellent catalytic activity toward hydrogen peroxide generation in enzymatic reaction between glucose oxidase and glucose, which would enable sensitive determination of glucose. Under the optimum condition, the linear response range of glucose was found to be 2.25 × 10(-6) to 1.75 × 10(-4 ) mol L(-1), and the detection limit (defined as the concentration that could be detected at the signal-to-noise ratio of 3) was 1.00 × 10(-6) mol L(-1). The CL biosensor exhibited good storage stability, i.e., 80% of its initial response was retained after 10 days storage at pH 7.0. The present CL biosensor has been used to determine the glucose concentrations in real serum and urine samples with satisfactory results. Copyright © 2011 Elsevier B.V. All rights reserved.

Capillary electrophoresis method with UV-detection for analysis of free amino acids concentrations in food.

PubMed

Omar, Mei Musa Ali; Elbashir, Abdalla Ahmed; Schmitz, Oliver J

2017-01-01

Simple and inexpensive capillary electrophoresis with UV-detection method (CE-UV) was optimized and validated for determination of six amino acids namely (alanine, asparagine, glutamine, proline, serine and valine) for Sudanese food. Amino acids in the samples were derivatized with 4-chloro-7-nitro-2,1,3-benzoxadiazole (NBD-Cl) prior to CE-UV analysis. Labeling reaction conditions (100mM borate buffer at pH 8.5, labeling reaction time 60min, temperature 70°C and NBD-Cl concentration 40mM) were systematically investigated. The optimal conditions for the separation were 100mM borate buffer at pH 9.7 and detected at 475nm. The method was validated in terms of linearity, limit of detection (LOD), limit of quantification (LOQ), precision (repeatability) (RSD%) and accuracy (recovery). Good linearity was achieved for all amino acids (r(2)>0.9981) in the concentration range of 2.5-40mg/L. The LODs in the range of 0.32-0.56mg/L were obtained. Recoveries of amino acids ranging from 85% to 108%, (n=3) were obtained. The validated method was successfully applied for the determination of amino acids for Sudanese food samples. Copyright © 2016 Elsevier Ltd. All rights reserved.

Detection of explosives using negative ion mobility spectrometry in air based on dopant-assisted thermal ionization.

PubMed

Shahraki, Hassan; Tabrizchi, Mahmoud; Farrokhpor, Hossein

2018-05-26

The ionization source is an essential component of most explosive detectors based on negative ion mobility spectrometry. Conventional ion sources suffer from such inherent limitations as special safety regulations on radioactive sources or generating interfering ions (for non-radioactive sources) such as corona discharge operating in the air. In this study, a new negative ion source is introduced for ion mobility spectrometry that is based on thermal ionization and operates in the air, applicable to explosives detection. Our system consists of a heating filament powered by an isolated power supply connected to negative high voltage. The ionization is assisted by doping chlorinated compounds in the gas phase using chlorinated hydrocarbons in contact with the heating element to yield Cl - reactant ions. Several chlorinated hydrocarbons are evaluated as the reagent chemicals for providing Cl- reactant ions, of which CCl 4 is identified as the best ionizing reagent. The ion source is evaluated by recording the ion mobility spectra of common explosives, including TNT, RDX, and PETN in the air. A detection limit of 150 pg is obtained for TNT. Compared to other ionization sources, the new source is found to be low-cost, simple, and long-lived, making it suited to portable explosives detection devices. Copyright © 2018 Elsevier B.V. All rights reserved.

NaNO3/NaCl Oxidant and Polyethylene Glycol (PEG) Capped Gold Nanoparticles (AuNPs) as a Novel Green Route for AuNPs Detection in Electrochemical Biosensors.

PubMed

López-Marzo, Adaris M; Hoyos-de-la-Torre, Raquel; Baldrich, Eva

2018-03-20

Gold nanoparticles (AuNPs) have been exploited as signal-producing tags in electrochemical biosensors. However, the electrochemical detection of AuNPs is currently performed using corrosive acid solutions, which may raise health and environmental concerns. Here, oxidant salts, and specifically the environmentally friendly and occupational safe NaNO 3 /NaCl mixture, have been evaluated for the first time as potential alternatives to the acid solutions traditionally used for AuNPs electrooxidation. In addition, a new strategy to improve the sensitivity of the biosensor through PEG-based ligand exchange to produce less compact and easier to oxidize AuNPs immunoconjugates is presented too. As we show, the electrochemical immunosensor using NaNO 3 /NaCl measurement solution for AuNPs electrooxidation and detection, coupled to the employment of PEG-capped nanoimmunoconjugates, produced results comparable to classical HCl detection. The procedure developed was next tested for human matrix metallopeptidase-9 (hMMP9) analysis, exhibiting a 0.18-23 ng/mL linear range, a detection limit of 0.06 ng/mL, and recoveries between 95 and 105% in spiked human plasma. These results show that the procedure developed is applicable to the analysis of protein biomarkers in blood plasma and could contribute to the development of more environmentally friendly AuNP-based electrochemical biosensors.

ClO radical yields in the reaction of O(1D) with Cl2, HCl, chloromethanes, and chlorofluoromethanes.

PubMed

Feierabend, Karl J; Papanastasiou, Dimitrios K; Burkholder, James B

2010-11-18

Absolute ClO radical product yields in the gas-phase reactions of O((1)D) with Cl(2), HCl, CCl(4), CHCl(3), CH(2)Cl(2), CH(3)Cl, CFCl(3), CF(2)Cl(2), CF(3)Cl, CHFCl(2), and CHF(2)Cl are reported. Product yields were measured using pulsed-laser photolysis of O(3) to produce O((1)D) in the presence of excess reactant combined with dual wavelength differential cavity ring-down spectroscopic detection of the ClO radical. ClO radical absorption cross sections for the A(2)Π(v = 10) ← X(2)Π(v = 0) transition band head near 280 nm were determined between 200 and 296 K as part of this work. The ClO product yields obtained at room temperature were Cl(2) (0.77 ± 0.10), HCl (0.20 ± 0.04), CCl(4) (0.79 ± 0.04), CHCl(3) (0.77 ± 0.04), CH(2)Cl(2) (0.73 ± 0.04), CH(3)Cl (0.46 ± 0.06), CFCl(3) (0.79 ± 0.04), CF(2)Cl(2) (0.76 ± 0.06), CF(3)Cl (0.82 ± 0.06), CHFCl(2) (0.73 ± 0.05), and CHF(2)Cl (0.56 ± 0.03), where the quoted error limits are 2σ of the measurement precision. ClO product yields in the O((1)D) + Cl(2) and CFCl(3) reactions were found to be independent of temperature between 200 and 296 K, within the precision of the measurements. The absolute ClO yields obtained in this study are compared with previously reported values determined using relative and indirect methods.

Determination of L-phenylalanine on-line based on molecularly imprinted polymeric microspheres and flow injection chemiluminescence

NASA Astrophysics Data System (ADS)

Qiu, Huamin; Xi, Yulei; Lu, Fuguang; Fan, Lulu; Luo, Chuannan

2012-02-01

A novel molecular imprinting-chemiluminescence (MIP-CL) sensor for the determination of L-phenylalanine (Phe) using molecularly imprinted polymer (MIP) as recognition element is reported. The Phe-MIP was synthesized using acrylamide (AM) as functional monomer and ethylene glycol dimethacrylate (EGDMA) as cross-linker, 2,2-azobisisobutyronitrile (AIBN) as initiator and the polymers' properties were characterized. Then the synthesized MIP was employed as recognition element by packing into flow cell to establish a novel flow injection CL sensor. The CL intensity responded linearly to the concentration of Phe in the range 1.3 × 10 -6 to 5.44 × 10 -4 mol/L with a detection limit of 6.23 × 10 -7 mol/L (3 σ), which is lower than that of conventional methods. The sensor is reusable and has a great improvement in sensitivity and selectivity for CL analysis. As a result, the new MIP-CL sensor had been successfully applied to the determination of Phe in samples.

Composition and source of salinity of ore-bearing fluids in Cu-Au systems of the Carajás Mineral Province, Brazil

USGS Publications Warehouse

Xavier, Roberto; Rusk, Brian; Emsbo, Poul; Monteiro, Lena

2009-01-01

The composition and Cl/Br – NaCl ratios of highly saline aqueous inclusions from large tonnage (> 100 t) IOCG deposits (Sossego, Alvo 118, and Igarapé Bahia) and a Paleoproterozoic intrusion-related Cu-Au-(Mo-W-Bi-Sn) deposit (Breves; < 50 Mt)) in the Carajás Mineral Province have been analysed by LA-ICP-MS and ion chromatography. In both Cu-Au systems, brine inclusions are Ca-dominated (5 to 10 times more than in porphyry Cu-Au fluids), and contain percent level concentrations of Na and K. IOCG inclusion fluids, however, contain higher Sr, Ba, Pb, and Zn concentrations, but significantly less Bi, than the intrusion-related Breves inclusion fluids. Cu is consistently below detection limits in brine inclusions from the IOCG and intrusion-related systems and Fe was not detected in the latter. Cl/Br and Na/Cl ratios of the IOCG inclusion fluids range from entirely evaporative brines (bittern fluids; e.g. Igarapé Bahia and Alvo 118) to values that indicate mixing with magma-derived brines. Cl/Br and Na/Cl ratios of the Breves inclusion fluids strongly suggest the involvement of magmatic brines, but that possibly also incorporated bittern fluids. Collectively, these data demonstrate that residual evaporative and magmatic brines were important components of the fluid regime involved in the formation of Cu-Au systems in the Carajás Mineral Province.

Chitosan-induced Au/Ag nanoalloy dispersed in IL and application in fabricating an ultrasensitive glucose biosensor based on luminol-H₂O₂-Cu²⁺/IL chemiluminescence system.

PubMed

Chaichi, M J; Alijanpour, S O

2014-11-01

A novel glucose biosensor based on the chemiluminescence (CL) detection of enzymatically generated hydrogen peroxide (H₂O₂) was constructed by one covalent immobilization of glucose oxidase (GOD) in glutaraldehyde-functionalized glass cell. In following, chitosan-induced Au/Ag nanoparticles dispersed in ion liquid (IL) were synthesised and immobilized on it. Herein, chitosan molecules acted as both the reducing and stabilizing agent for the preparation of NPs and also, as a coupling agent GOD and Au/Ag alloy NPs. In addition to catalyze luminol CL reaction, these NPs offered excellent catalytic activity toward hydrogen peroxide generation in enzymatic reaction between GOD and glucose. The used IL in fabrication of biosensor increased its stability. Also, IL alongside Cu(2+) accelerated enzymatic and CL reaction kinetic, and decreased luminol CL reaction optimum pH to 7.5 which would enable sensitive and precision determination of glucose. Under optimum condition, linear response range of glucose was found to be 1.0 × 10(-6)-7.5 × 10(-3)M, and detection limit was 4.0 × 10(-7)M. The CL biosensor exhibited good storage stability, i.e., 90% of its initial response was retained after 2 months storage at pH 7.0. The present CL biosensor has been applied satisfactory to analysis of glucose in real serum and urine samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Environmental monitoring of bleached kraft pulp mill chlorophenolic compounds in a northern Canadian river system.

PubMed

Owens, J W; Swanson, S M; Birkholz, D A

1994-07-01

The environmental transport of pulp mill effluent compounds and the exposure of two fish species has been monitored by parallel analyses of effluent, water column and suspended sediment samples, and fish bile and muscle. Compounds analyzed included over 20 chlorophenolic compounds and 12 fatty and resin acids. The concentration of chlorophenols varied with seasonal river flows and mill process changes such as the substitution of chlorine dioxide (ClO2) for chlorine gas (Cl2) in the bleach plant. At 100% (ClO2) substitution, the effluent and the water column concentrations of most chlorophenolics approached the analytical detection limits of 0.1-1 parts per billion. Chlorophenolic and fatty/resin acid compounds were detected in the bile of both mountain whitefish (Prosopium williamsoni) and longnose sucker (Catostomus catostomus), but were rarely detected in fillets. Fish bile concentrations were observed in an apparent spatial gradient as far as 230 km downstream of the mill. A depuration experiment with fish held in uncontaminated water for eight days indicated a rapid decrease in chlorophenol levels. These observations corroborate previous investigations that chlorophenolic compounds are rapidly excreted and can be used as sensitive markers for recent exposure to mill effluents.

Luminol, horseradish peroxidase, and glucose oxidase ternary functionalized graphene oxide for ultrasensitive glucose sensing.

PubMed

Li, Fang; Ma, Wenjing; Liu, Jiachang; Wu, Xiang; Wang, Yan; He, Jianbo

2018-01-01

Luminol, horseradish peroxidase (HRP), and glucose oxidase (GOx) ternary functionalized graphene oxide (HRP/GOx-luminol-GO) with excellent chemiluminescence (CL) activity and specific enzymatic property was prepared via a simple and general strategy for the first time. In this approach, luminol functionalized GO (luminol-GO) was prepared by gently stirring GO with luminol. Then HRP and GOx were further co-immobilized onto the surface of luminol-GO by storing HRP and GOx with luminol-GO at 4 °C overnight, to form HRP/GOx-luminol-GO bionanocomposites. The synthesized HRP/GOx-luminol-GO could react with H 2 O 2 generated from GOx catalyzed glucose oxidization reaction, to produce strong CL emission in the presence of co-immobilized HRP. Thus, we developed an ultrasensitive, homogeneous, reagentless, selective, and simple CL sensing system for glucose detection. The resulting biosensors exhibited ultra-wide linear range from 5.0 nM to 5.0 mM, and an ultra-low detection limit of 1.2 nM, which was more than 3 orders of magnitude lower than previously reported methods. Furthermore, the sensing system was successfully applied for the detection of glucose in human blood samples.

Sensitive and selective determination of fluvoxamine maleate using a sensitive chemiluminescence system based on the alkaline permanganate-Rhodamine B-gold nanoparticles reaction.

PubMed

Hassanzadeh, Javad; Amjadi, Mohammad

2015-06-01

A high-yield chemiluminescence (CL) system based on the alkaline permanganate-Rhodamine B reaction was developed for the sensitive determination of fluvoxamine maleate (Flu). Rhodamine B is oxidized by alkaline KMnO4 and a weak CL emission is produced. It was demonstrated that gold nanoparticles greatly enhance this CL emission due to their interaction with Rhodamine B molecules. It is also observed that sodium dodecyl sulfate, an anionic surfactant, can strongly increase this enhancement. In addition, it was demonstrated that a notable decrease in the CL intensity is observed in the presence of Flu. This may be related to Flu oxidation with KMnO4 . There is a linear relationship between the decrease in CL intensity and the Flu concentration over a range of 2-300 µg/L. A new simple, rapid and sensitive CL method was developed for the determination of Flu with a detection limit (3s) of 1.35 µg/L. The proposed method was used for the determination of Flu in pharmaceutical and urine samples. Copyright © 2014 John Wiley & Sons, Ltd.

A highly sensitive and temporal visualization system for gaseous ethanol with chemiluminescence enhancer.

PubMed

Arakawa, Takahiro; Ando, Eri; Wang, Xin; Kumiko, Miyajima; Kudo, Hiroyuki; Saito, Hirokazu; Mitani, Tomoyo; Takahashi, Mitsuo; Mitsubayashi, Kohji

2012-01-01

A two-dimensional gaseous ethanol visualization system has been developed and demonstrated using a horseradish peroxidase-luminol-hydrogen peroxide system with high-purity luminol solution and a chemiluminescence (CL) enhancer. This system measures ethanol concentrations as intensities of CL via the luminol reaction. CL was emitted when the gaseous ethanol was injected onto an enzyme-immobilized membrane, which was employed as a screen for two-dimensional gas visualization. The average intensity of CL on the substrate was linearly related to the concentration of standard ethanol gas. These results were compared with the CL intensity of the CCD camera recording image in the visualization system. This system is available for gas components not only for spatial but also for temporal analysis in real time. A high-purity sodium salt HG solution (L-HG) instead of standard luminol solution and an enhancer, eosin Y (EY) solution, were adapted for improvement of CL intensity of the system. The visualization of gaseous ethanol was achieved at a detection limit of 3 ppm at optimized concentrations of L-HG solution and EY. Copyright © 2011 John Wiley & Sons, Ltd.

A novel luminol chemiluminescent method catalyzed by silver/gold alloy nanoparticles for determination of anticancer drug flutamide.

PubMed

Chaichi, Mohammad Javad; Azizi, Seyed Naser; Heidarpour, Maryam

2013-12-01

It was found that silver/gold alloy nanoparticles enhance the chemiluminescence (CL) of the luminol-H2O2 system in alkaline solution. The studies of UV-Vis spectra, CL spectra, effects of concentrations luminol, hydrogen peroxide and silver/gold alloy nanoparticles solutions were carried out to explore the CL enhancement mechanism. Flutamide was found to quench the CL signals of the luminol-H2O2 reaction catalyzed by silver/gold alloy nanoparticles, which made it applicable for the determination of flutamide. Under the optimum conditions, the CL intensity is proportional to the concentration of the flutamide in solution over the range 5.0 × 10(-7) to 1.0 × 10(-4)mol L(-1). Detection limit was obtained 1.2 × 10(-8)mol L(-1)and the relative standard deviation (RSD) γ5%. This work is introduced as a new method for the determination of flutamide in commercial tablets. Box-Behnken experimental design is applied to investigate and validate the CL measurement parameters. Copyright © 2013 Elsevier B.V. All rights reserved.

Inactivation of feline calicivirus, a norovirus surrogate, by chlorine dioxide gas.

PubMed

Morino, Hirofumi; Fukuda, Toshiaki; Miura, Takanori; Lee, Cheolsung; Shibata, Takashi; Sanekata, Takeshi

2009-12-01

The efficacy of gaseous chlorine dioxide (ClO2) against feline calicivirus (FCV), a norovirus surrogate, in the dry and the wet states on a hard surface was evaluated. We demonstrated that low-concentration ClO2 gas (mean 0.08 ppm, 0.22 microg/I) could inactivate FCV in the wet state with 0.5% fetal bovine serum (FBS) within 6 h in 45 to 55% relative humidity (RH) (> 3 log10 reductions) and FCV in the dry state with 2% FBS (percentage of FBS in the viral suspension) within 10 h in 75 to 85% RH (> 3 log10 reductions) at 20 degrees C, respectively. Furthermore, a < 0.3 ppm concentration of ClO2 gas (mean 0.26 ppm, 0.73 microg/l) could inactivate (below the detection limit) FCV in the dry state with 5% FBS within 24 h in 75 to 85% RH at 20 degrees C. In contrast, in 45 to 55% RH at 20 degrees C, ClO2 gas had little effect even when the FCV in the dry state was exposed to high-concentration ClO2 (mean 8 ppm, 22.4 microg/l) for 24 h. These results suggest that humidity plays an important role in the inactivation by ClO2 gas of FCV in the dry state. According to the International Chemical Safety Card, threshold limit values for ClO2 gas are 0.1 ppm as an 8-h time-weighted average and 0.3 ppm as a 15 min short-term exposure limit. From these data, we propose that the treatment of wet areas of human activity such as kitchens, toilets, etc., with low-concentration ClO2 gas would be useful for reducing the risk of infection by noroviruses (NV) without adverse effects. In addition, we believe that the application of a combination of a < 0.3 ppm concentration of ClO2 gas and a humidifier in places without human activity may make it possible to inactivate NV in the dry state on any surface within a contaminated room without serious adverse effects.

Is there any chlorine monoxide in the stratosphere?

NASA Technical Reports Server (NTRS)

Mumma, M. J.; Rogers, J. D.; Kostiuk, T.; Deming, D.; Hillman, J. J.; Zipoy, D.

1983-01-01

A ground-based search for stratospheric 35-ClO was carried out using an infrared heterodyne spectrometer in the solar absorption mode. Lines due to stratospheric HNO3 and tropospheric OCS were detected at about 0.2 percent absorptance levels, but the expected 0.1 percent lines of ClO in this same region were not seen. We find that stratospheric ClO is at least a factor of seven less abundant than is indicated by in situ measurements, and we set an upper limit of 2.3 x 10 to the 13th molecules/sq cm at the 95 percent confidence level for the integrated vertical column density of ClO. Our results imply that the release of chlorofluorocarbons may be significantly less important for the destruction of stratospheric ozone (O3) than is currently thought. Previously announced in STAR as N83-27518

Artificial enzyme mimics for catalysis and double natural enzyme co-immobilization.

PubMed

Li, Xiaohua; Zhang, Zhujun; Li, Yongbo

2014-02-01

This work presents a new chemiluminescent (CL) probe array assay. The new type CL probe array is based on enzyme mimics of Co3O4-SiO2 mesoporous nanocomposite material, which not only have an excellent catalytic effect on the luminol-H2O2 CL reaction in an alkaline medium but also can be used for the immobilization of enzymes. The linear range of the lactose concentration is 3.0 × 10(-7) to 1.0 × 10(-5) g mL(-1) and the detection limit is 6.9 × 10(-8) g mL(-1). β-Galactosidase and glucose oxidase were selected as a model for enzyme assays to demonstrate the applicability of Co3O4-SiO2 mesoporous nanocomposite material in multienzyme immobilization. The novel bifunctional CL probe array has been successfully applied to the determination of lactose in milk.

The Salty Scrambled Egg: Detection of NaCl Toward CRL 2688

NASA Astrophysics Data System (ADS)

Highberger, J. L.; Thomson, K. J.; Young, P. A.; Arnett, D.; Ziurys, L. M.

2003-08-01

NaCl has been detected toward the circumstellar envelope of the post-AGB star CRL 2688 using the IRAM 30 m telescope, the first time this molecule has been identified in a source other than IRC +10216. The J=7-->6, 11-->10, 12-->11, and 18-->17 transitions of NaCl at 1, 2, and 3 mm have been observed, as well as the J=8-->7 line of the 37Cl isotopomer. The J=12-->11 line was also measured at the ARO 12 m telescope. An unsuccessful search was additionally conducted for AlCl toward CRL 2688, although in the process new transitions of NaCN were observed. Both NaCl and NaCN were found to be present in the AGB remnant wind, as suggested by their U-shaped line profiles, indicative of emission arising from an optically thin, extended shell-like source of radius ~10"-12". These data contrast with past results in IRC +10216, where the distribution of both molecules is confined to within a few arcseconds of the star. A high degree of excitation is required for the transitions observed for NaCl and NaCN; therefore, these two species likely arise in the region where the high-velocity outflow has collided with the remnant wind. Here the effects of shocks and clumping due to Rayleigh-Taylor instabilities have raised the densities and temperatures significantly. The shell source is thus likely to be clumpy and irregular. The chemistry producing the sodium compounds is consequently more complex than simple LTE formation. Abundances of NaCl and NaCN, relative to H2, are f~1.6×10-10 and ~5.2×10-9, respectively, while the upper limit to AlCl is f<2×10-9. These values differ substantially from those in IRC +10216, where AlCl has an abundance near 10-7. The NaCl observations additionally indicate a chlorine isotope ratio of 35Cl/37Cl=2.1+/-0.8 in CRL 2688, suggestive of s-process enhancement of chlorine 37.

Directional Limits on Persistent Gravitational Waves Using LIGO S5 Science Data

NASA Astrophysics Data System (ADS)

Abadie, J.; Abbott, B. P.; Abbott, R.; Abernathy, M.; Accadia, T.; Acernese, F.; Adams, C.; Adhikari, R.; Ajith, P.; Allen, B.; Allen, G. S.; Amador Ceron, E.; Amin, R. S.; Anderson, S. B.; Anderson, W. G.; Antonucci, F.; Arain, M. A.; Araya, M. C.; Aronsson, M.; Arun, K. G.; Aso, Y.; Aston, S. M.; Astone, P.; Atkinson, D.; Aufmuth, P.; Aulbert, C.; Babak, S.; Baker, P.; Ballardin, G.; Ballmer, S.; Barker, D.; Barnum, S.; Barone, F.; Barr, B.; Barriga, P.; Barsotti, L.; Barsuglia, M.; Barton, M. A.; Bartos, I.; Bassiri, R.; Bastarrika, M.; Bauchrowitz, J.; Bauer, Th. S.; Behnke, B.; Beker, M. G.; Belletoile, A.; Benacquista, M.; Bertolini, A.; Betzwieser, J.; Beveridge, N.; Beyersdorf, P. T.; Bigotta, S.; Bilenko, I. A.; Billingsley, G.; Birch, J.; Birindelli, S.; Biswas, R.; Bitossi, M.; Bizouard, M. A.; Black, E.; Blackburn, J. K.; Blackburn, L.; Blair, D.; Bland, B.; Blom, M.; Boccara, C.; Bock, O.; Bodiya, T. P.; Bondarescu, R.; Bondu, F.; Bonelli, L.; Bonnand, R.; Bork, R.; Born, M.; Bose, S.; Bosi, L.; Bouhou, B.; Boyle, M.; Braccini, S.; Bradaschia, C.; Brady, P. R.; Braginsky, V. B.; Brau, J. E.; Breyer, J.; Bridges, D. O.; Brillet, A.; Brinkmann, M.; Brisson, V.; Britzger, M.; Brooks, A. F.; Brown, D. A.; Budzyński, R.; Bulik, T.; Bulten, H. J.; Buonanno, A.; Burguet-Castell, J.; Burmeister, O.; Buskulic, D.; Buy, C.; Byer, R. L.; Cadonati, L.; Cagnoli, G.; Cain, J.; Calloni, E.; Camp, J. B.; Campagna, E.; Campsie, P.; Cannizzo, J.; Cannon, K.; Canuel, B.; Cao, J.; Capano, C.; Carbognani, F.; Caride, S.; Caudill, S.; Cavaglià, M.; Cavalier, F.; Cavalieri, R.; Cella, G.; Cepeda, C.; Cesarini, E.; Chalermsongsak, T.; Chalkley, E.; Charlton, P.; Chassande-Mottin, E.; Chelkowski, S.; Chen, Y.; Chincarini, A.; Christensen, N.; Chua, S. S. Y.; Chung, C. T. Y.; Clark, D.; Clark, J.; Clayton, J. H.; Cleva, F.; Coccia, E.; Colacino, C. N.; Colas, J.; Colla, A.; Colombini, M.; Conte, R.; Cook, D.; Corbitt, T. R.; Cornish, N.; Corsi, A.; Costa, C. A.; Coulon, J.-P.; Coward, D. M.; Coyne, D. C.; Creighton, J. D. E.; Creighton, T. D.; Cruise, A. M.; Culter, R. M.; Cumming, A.; Cunningham, L.; Cuoco, E.; Dahl, K.; Danilishin, S. L.; Dannenberg, R.; D'Antonio, S.; Danzmann, K.; Das, K.; Dattilo, V.; Daudert, B.; Davier, M.; Davies, G.; Davis, A.; Daw, E. J.; Day, R.; Dayanga, T.; de Rosa, R.; Debra, D.; Degallaix, J.; Del Prete, M.; Dergachev, V.; Derosa, R.; Desalvo, R.; Devanka, P.; Dhurandhar, S.; di Fiore, L.; di Lieto, A.; di Palma, I.; di Paolo Emilio, M.; di Virgilio, A.; Díaz, M.; Dietz, A.; Donovan, F.; Dooley, K. L.; Doomes, E. E.; Dorsher, S.; Douglas, E. S. D.; Drago, M.; Drever, R. W. P.; Driggers, J. C.; Dueck, J.; Dumas, J.-C.; Eberle, T.; Edgar, M.; Edwards, M.; Effler, A.; Ehrens, P.; Engel, R.; Etzel, T.; Evans, M.; Evans, T.; Fafone, V.; Fairhurst, S.; Fan, Y.; Farr, B. F.; Fazi, D.; Fehrmann, H.; Feldbaum, D.; Ferrante, I.; Fidecaro, F.; Finn, L. S.; Fiori, I.; Flaminio, R.; Flanigan, M.; Flasch, K.; Foley, S.; Forrest, C.; Forsi, E.; Fotopoulos, N.; Fournier, J.-D.; Franc, J.; Frasca, S.; Frasconi, F.; Frede, M.; Frei, M.; Frei, Z.; Freise, A.; Frey, R.; Fricke, T. T.; Friedrich, D.; Fritschel, P.; Frolov, V. V.; Fulda, P.; Fyffe, M.; Galimberti, M.; Gammaitoni, L.; Garofoli, J. A.; Garufi, F.; Gemme, G.; Genin, E.; Gennai, A.; Gholami, I.; Ghosh, S.; Giaime, J. A.; Giampanis, S.; Giardina, K. D.; Giazotto, A.; Gill, C.; Goetz, E.; Goggin, L. M.; González, G.; Gorodetsky, M. L.; Goßler, S.; Gouaty, R.; Graef, C.; Granata, M.; Grant, A.; Gras, S.; Gray, C.; Greenhalgh, R. J. S.; Gretarsson, A. M.; Greverie, C.; Grosso, R.; Grote, H.; Grunewald, S.; Guidi, G. M.; Gustafson, E. K.; Gustafson, R.; Hage, B.; Hall, P.; Hallam, J. M.; Hammer, D.; Hammond, G.; Hanks, J.; Hanna, C.; Hanson, J.; Harms, J.; Harry, G. M.; Harry, I. W.; Harstad, E. D.; Haughian, K.; Hayama, K.; Hayau, J.-F.; Hayler, T.; Heefner, J.; Heitmann, H.; Hello, P.; Heng, I. S.; Heptonstall, A. W.; Hewitson, M.; Hild, S.; Hirose, E.; Hoak, D.; Hodge, K. A.; Holt, K.; Hosken, D. J.; Hough, J.; Howell, E. J.; Hoyland, D.; Huet, D.; Hughey, B.; Husa, S.; Huttner, S. H.; Huynh–Dinh, T.; Ingram, D. R.; Inta, R.; Isogai, T.; Ivanov, A.; Jaranowski, P.; Johnson, W. W.; Jones, D. I.; Jones, G.; Jones, R.; Ju, L.; Kalmus, P.; Kalogera, V.; Kandhasamy, S.; Kanner, J. B.; Katsavounidis, E.; Kawabe, K.; Kawamura, S.; Kawazoe, F.; Kells, W.; Keppel, D. G.; Khalaidovski, A.; Khalili, F. Y.; Khazanov, E. A.; Kim, H.; King, P. J.; Kinzel, D. L.; Kissel, J. S.; Klimenko, S.; Kondrashov, V.; Kopparapu, R.; Koranda, S.; Kowalska, I.; Kozak, D.; Krause, T.; Kringel, V.; Krishnamurthy, S.; Krishnan, B.; Królak, A.; Kuehn, G.; Kullman, J.; Kumar, R.; Kwee, P.; Landry, M.; Lang, M.; Lantz, B.; Lastzka, N.; Lazzarini, A.; Leaci, P.; Leong, J.; Leonor, I.; Leroy, N.; Letendre, N.; Li, J.; Li, T. G. F.; Liguori, N.; Lin, H.; Lindquist, P. E.; Lockerbie, N. A.; Lodhia, D.; Lorenzini, M.; Loriette, V.; Lormand, M.; Losurdo, G.; Lu, P.; Luan, J.; Lubinski, M.; Lucianetti, A.; Lück, H.; Lundgren, A. D.; Machenschalk, B.; Macinnis, M.; Mageswaran, M.; Mailand, K.; Majorana, E.; Mak, C.; Maksimovic, I.; Man, N.; Mandel, I.; Mandic, V.; Mantovani, M.; Marchesoni, F.; Marion, F.; Márka, S.; Márka, Z.; Maros, E.; Marque, J.; Martelli, F.; Martin, I. W.; Martin, R. M.; Marx, J. N.; Mason, K.; Masserot, A.; Matichard, F.; Matone, L.; Matzner, R. A.; Mavalvala, N.; McCarthy, R.; McClelland, D. E.; McGuire, S. C.; McIntyre, G.; McIvor, G.; McKechan, D. J. A.; Meadors, G.; Mehmet, M.; Meier, T.; Melatos, A.; Melissinos, A. C.; Mendell, G.; Menéndez, D. F.; Mercer, R. A.; Merill, L.; Meshkov, S.; Messenger, C.; Meyer, M. S.; Miao, H.; Michel, C.; Milano, L.; Miller, J.; Minenkov, Y.; Mino, Y.; Mitra, S.; Mitrofanov, V. P.; Mitselmakher, G.; Mittleman, R.; Moe, B.; Mohan, M.; Mohanty, S. D.; Mohapatra, S. R. P.; Moraru, D.; Moreau, J.; Moreno, G.; Morgado, N.; Morgia, A.; Morioka, T.; Mors, K.; Mosca, S.; Moscatelli, V.; Mossavi, K.; Mours, B.; Mow–Lowry, C. M.; Mueller, G.; Mukherjee, S.; Mullavey, A.; Müller-Ebhardt, H.; Munch, J.; Murray, P. G.; Nash, T.; Nawrodt, R.; Nelson, J.; Neri, I.; Newton, G.; Nishizawa, A.; Nocera, F.; Nolting, D.; Ochsner, E.; O'Dell, J.; Ogin, G. H.; Oldenburg, R. G.; O'Reilly, B.; O'Shaughnessy, R.; Osthelder, C.; Ottaway, D. J.; Ottens, R. S.; Overmier, H.; Owen, B. J.; Page, A.; Pagliaroli, G.; Palladino, L.; Palomba, C.; Pan, Y.; Pankow, C.; Paoletti, F.; Papa, M. A.; Pardi, S.; Pareja, M.; Parisi, M.; Pasqualetti, A.; Passaquieti, R.; Passuello, D.; Patel, P.; Pathak, D.; Pedraza, M.; Pekowsky, L.; Penn, S.; Peralta, C.; Perreca, A.; Persichetti, G.; Pichot, M.; Pickenpack, M.; Piergiovanni, F.; Pietka, M.; Pinard, L.; Pinto, I. M.; Pitkin, M.; Pletsch, H. J.; Plissi, M. V.; Poggiani, R.; Postiglione, F.; Prato, M.; Predoi, V.; Price, L. R.; Prijatelj, M.; Principe, M.; Prix, R.; Prodi, G. A.; Prokhorov, L.; Puncken, O.; Punturo, M.; Puppo, P.; Quetschke, V.; Raab, F. J.; Rabeling, D. S.; Radke, T.; Radkins, H.; Raffai, P.; Rakhmanov, M.; Rankins, B.; Rapagnani, P.; Raymond, V.; Re, V.; Reed, C. M.; Reed, T.; Regimbau, T.; Reid, S.; Reitze, D. H.; Ricci, F.; Riesen, R.; Riles, K.; Roberts, P.; Robertson, N. A.; Robinet, F.; Robinson, C.; Robinson, E. L.; Rocchi, A.; Roddy, S.; Röver, C.; Rolland, L.; Rollins, J.; Romano, J. D.; Romano, R.; Romie, J. H.; Rosińska, D.; Rowan, S.; Rüdiger, A.; Ruggi, P.; Ryan, K.; Sakata, S.; Sakosky, M.; Salemi, F.; Sammut, L.; Sancho de La Jordana, L.; Sandberg, V.; Sannibale, V.; Santamaría, L.; Santostasi, G.; Saraf, S.; Sassolas, B.; Sathyaprakash, B. S.; Sato, S.; Satterthwaite, M.; Saulson, P. R.; Savage, R.; Schilling, R.; Schnabel, R.; Schofield, R. M. S.; Schulz, B.; Schutz, B. F.; Schwinberg, P.; Scott, J.; Scott, S. M.; Searle, A. C.; Seifert, F.; Sellers, D.; Sengupta, A. S.; Sentenac, D.; Sergeev, A.; Shaddock, D. A.; Shapiro, B.; Shawhan, P.; Shoemaker, D. H.; Sibley, A.; Siemens, X.; Sigg, D.; Singer, A.; Sintes, A. M.; Skelton, G.; Slagmolen, B. J. J.; Slutsky, J.; Smith, J. R.; Smith, M. R.; Smith, N. D.; Somiya, K.; Sorazu, B.; Speirits, F. C.; Sperandio, L.; Stein, A. J.; Stein, L. C.; Steinlechner, S.; Steplewski, S.; Stochino, A.; Stone, R.; Strain, K. A.; Strigin, S.; Stroeer, A. S.; Sturani, R.; Stuver, A. L.; Summerscales, T. Z.; Sung, M.; Susmithan, S.; Sutton, P. J.; Swinkels, B.; Szokoly, G. P.; Talukder, D.; Tanner, D. B.; Tarabrin, S. P.; Taylor, J. R.; Taylor, R.; Thomas, P.; Thorne, K. A.; Thorne, K. S.; Thrane, E.; Thüring, A.; Titsler, C.; Tokmakov, K. V.; Toncelli, A.; Tonelli, M.; Torre, O.; Torres, C.; Torrie, C. I.; Tournefier, E.; Travasso, F.; Traylor, G.; Trias, M.; Trummer, J.; Tseng, K.; Turner, L.; Ugolini, D.; Urbanek, K.; Vahlbruch, H.; Vaishnav, B.; Vajente, G.; Vallisneri, M.; van den Brand, J. F. J.; van den Broeck, C.; van der Putten, S.; van der Sluys, M. V.; van Veggel, A. A.; Vass, S.; Vaulin, R.; Vavoulidis, M.; Vecchio, A.; Vedovato, G.; Veitch, J.; Veitch, P. J.; Veltkamp, C.; Verkindt, D.; Vetrano, F.; Viceré, A.; Villar, A. E.; Vinet, J.-Y.; Vocca, H.; Vorvick, C.; Vyachanin, S. P.; Waldman, S. J.; Wallace, L.; Wanner, A.; Ward, R. L.; Was, M.; Wei, P.; Weinert, M.; Weinstein, A. J.; Weiss, R.; Wen, L.; Wen, S.; Wessels, P.; West, M.; Westphal, T.; Wette, K.; Whelan, J. T.; Whitcomb, S. E.; White, D.; Whiting, B. F.; Wilkinson, C.; Willems, P. A.; Williams, L.; Willke, B.; Winkelmann, L.; Winkler, W.; Wipf, C. C.; Wiseman, A. G.; Woan, G.; Wooley, R.; Worden, J.; Yakushin, I.; Yamamoto, H.; Yamamoto, K.; Yeaton-Massey, D.; Yoshida, S.; Yu, P.; Yvert, M.; Zanolin, M.; Zhang, L.; Zhang, Z.; Zhao, C.; Zotov, N.; Zucker, M. E.; Zweizig, J.

2011-12-01

The gravitational-wave (GW) sky may include nearby pointlike sources as well as stochastic backgrounds. We perform two directional searches for persistent GWs using data from the LIGO S5 science run: one optimized for pointlike sources and one for arbitrary extended sources. Finding no evidence to support the detection of GWs, we present 90% confidence level (C.L.) upper-limit maps of GW strain power with typical values between 2-20×10-50strain2Hz-1 and 5-35×10-49strain2Hz-1sr-1 for pointlike and extended sources, respectively. The latter result is the first of its kind. We also set 90% C.L. limits on the narrow-band root-mean-square GW strain from interesting targets including Sco X-1, SN 1987A and the Galactic center as low as ≈7×10-25 in the most sensitive frequency range near 160 Hz.

Limits on low-energy neutrino fluxes with the Mont Blanc liquid scintillator detector

NASA Astrophysics Data System (ADS)

Aglietta, M.; Antonioli, P.; Badino, G.; Bologna, G.; Castagnoli, C.; Castellina, A.; Dadykin, V. L.; Fulgione, W.; Galeotti, P.; Khalchukov, F. F.; Korolkova, E. V.; Kortchaguin, P. V.; Kortchaguin, V. B.; Kudryavtsev, V. A.; Malguin, A. S.; Periale, L.; Ryassny, V. G.; Ryazhskaya, O. G.; Saavedra, O.; Trinchero, G.; Vernetto, S.; Yakushev, V. F.; Zatsepin, G. T.

1992-11-01

The LSD liquid scintillation detector has been operating since 1985 as an underground neutrino observatory in the Mont Blanc Laboratory with the main objective of detecting antineutrino bursts from collapsing stars. In August 1988 the construction of an additional lead and borex paraffin shield considerably reduced the radioactive background and increased the sensitivity of the apparatus. In this way the search for steady fluxes of low-energy neutrinos of different flavours through their interactions with free protons and carbon nuclei of the scintillator was made possible. No evidence for a galactic collapse was observed during the whole period of measurement. The corresponding 90% c.l. upper limit on the galactic collapses rate is 0.45 y -1 for a burst duration of ΔT ⩽ 10 s. After analysing the last 3 years data, the following 90% c.l. upper limits on the steady neutrino and antineutrino fluxes were obtained:

The Effect of SnCl2/AmF Pretreatment on Short- and Long-Term Bond Strength to Eroded Dentin

PubMed Central

Zumstein, Katrin; Peutzfeldt, Anne; Lussi, Adrian

2018-01-01

This study investigated the effect of SnCl2/AmF pretreatment on short- and long-term bond strength of resin composite to eroded dentin mediated by two self-etch, MDP-containing adhesive systems. 184 dentin specimens were produced from extracted human molars. Half the specimens (n = 92) were artificially eroded, and half were left untreated. For both substrates, half the specimens were pretreated with SnCl2/AmF, and half were left untreated. The specimens were treated with Clearfil SE Bond or Scotchbond Universal prior to application of resin composite. Microtensile bond strength (μTBS) was measured after 24 h or 1 year. Failure mode was detected and EDX was performed. μTBS results were statistically analyzed (α = 0.05). μTBS was significantly influenced by the dentin substrate (eroded < noneroded dentin) and storage time (24 h > 1 year; p < 0.0001) but not by pretreatment with SnCl2/AmF or adhesive system. The predominant failure mode was adhesive failure at the dentin-adhesive interface. The content of Sn was generally below detection limit. Pretreatment with SnCl2/AmF did not influence short- and long-term bond strength to eroded dentin. Bond strength was reduced after storage for one year, was lower to eroded dentin than to noneroded dentin, and was similar for the two adhesive systems.

New Fluorescent and Colorimetric Chemosensor for Detection of Cyanide with High Selectivity and Sensitivity in Aqueous Media.

PubMed

Zali-Boeini, Hassan; Zareh Jonaghani, Mohammad

2017-05-01

A fluorescent and colorimetric chemosensor for detection of cyanide ion based on a styryl quinoline derivative has been designed and synthesized. The chemosensor (E)-2-(4-mercaptostyryl)quinolin-8-ol L showed high selectivity for detection of cyanide over other anions such as F¯, Cl¯, Br¯, I¯, NO 3 ¯, SCN¯, N 3 ¯, ClO 4 ¯, H 2 PO 4 ¯, AcO¯, HCO 3 ¯, SO 4 2 ¯ and HSO 4 ¯in aqueous solution. The chemosensor L displayed an immediate visible and fluorescence changes from nearly colorless to orange and greenish-blue to brick-red upon addition of cyanide ion respectively. It is more likely, these distinct changes can be attributed to hydrogen bonding interaction between phenol group and cyanide anion leading to a 1:1 binding stoichiometry following with deprotonation of phenol group. The detection limit for chemosensor L toward CN¯ was 2.73× 10 -8  M. Thus, the chemosensor can be used efficiently and selectively for detection and monitoring of small amounts of cyanide ion in aqueous media.

Polydimethylsiloxane microfluidic chemiluminescence immunodevice with the signal amplification strategy for sensitive detection of human immunoglobin G.

PubMed

Li, Huifang; Zhao, Mei; Liu, Wei; Chu, Weiru; Guo, Yumei

2016-01-15

A polydimethylsiloxane (PDMS) microfluidic chemiluminescence (CL) immunodevice for sensitive detection of human immunoglobin G (IgG) with the signal amplification strategy was developed in this work. The immunodevice was prepared by covalently immobilizing capture antibodies (Abs) on the silanized microchannel of microfluidic chip. Gold nanoparticles (AuNPs) functionalized with a high molar ratio of horseradish peroxidase (HRP) were used as an Ab label for signal amplification. Using a sandwich immunoassay, the multi-HRP conjugated AuNPs can catalyze the luminol-H2O2 CL system to achieve the high sensitivity. In addition, the double spiral flow-channel was adopted here, which can still contribute to the high sensitivity. Based on signal amplification strategy, the performance of human IgG tests revealed a lower detection limit (DL) of 0.03ng/mL and showed an increase of 7.4-fold in detection sensitivity compared to a commercial Ab-HRP conjugation. This microfluidic immunodevice can provide an alternative approach for sensitive detection of human IgG in the field of clinic diagnostic and therapeutic. Copyright © 2015 Elsevier B.V. All rights reserved.

Flow injection analysis of organic peroxide explosives using acid degradation and chemiluminescent detection of released hydrogen peroxide.

PubMed

Mahbub, Parvez; Zakaria, Philip; Guijt, Rosanne; Macka, Mirek; Dicinoski, Greg; Breadmore, Michael; Nesterenko, Pavel N

2015-10-01

The applicability of acid degradation of organic peroxides into hydrogen peroxide in a pneumatically driven flow injection system with chemiluminescence reaction with luminol and Cu(2+) as a catalyst (FIA-CL) was investigated for the fast and sensitive detection of organic peroxide explosives (OPEs). The target OPEs included hexamethylene triperoxide diamine (HMTD), triacetone triperoxide (TATP) and methylethyl ketone peroxide (MEKP). Under optimised conditions maximum degradations of 70% and 54% for TATP and HMTD, respectively were achieved at 162 µL min(-1), and 9% degradation for MEKP at 180 µL min(-1). Flow rates were precisely controlled in this single source pneumatic pressure driven multi-channel FIA system by model experiments on mixing of easily detectable component solutions. The linear range for detection of TATP, HMTD and H2O2 was 1-200 µM (r(2)=0.98-0.99) at both flow rates, while that for MEKP was 20-200 µM (r(2)=0.97) at 180 µL min(-1). The detection limits (LODs) obtained were 0.5 µM for TATP, HMTD and H2O2 and 10 µM for MEKP. The detection times varied from 1.5 to 3 min in this FIA-CL system. Whilst the LOD for H2O2 was comparable with those reported by other investigators, the LODs and analysis times for TATP and HMTD were superior, and significantly, this is the first time the detection of MEKP has been reported by FIA-CL. Copyright © 2015 Elsevier B.V. All rights reserved.

Total Acid Value Titration of Hydrotreated Biomass Fast Pyrolysis Oil: Determination of Carboxylic Acids and Phenolics with Multiple End-Point Detection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Christensen, E.; Alleman, T. L.; McCormick, R. L.

Total acid value titration has long been used to estimate corrosive potential of petroleum crude oil and fuel oil products. The method commonly used for this measurement, ASTM D664, utilizes KOH in isopropanol as the titrant with potentiometric end point determination by pH sensing electrode and Ag/AgCl reference electrode with LiCl electrolyte. A natural application of the D664 method is titration of pyrolysis-derived bio-oil, which is a candidate for refinery upgrading to produce drop in fuels. Determining the total acid value of pyrolysis derived bio-oil has proven challenging and not necessarily amenable to the methodology employed for petroleum products duemore » to the different nature of acids present. We presented an acid value titration for bio-oil products in our previous publication which also utilizes potentiometry using tetrabutylammonium hydroxide in place of KOH as the titrant and tetraethylammonium bromide in place of LiCl as the reference electrolyte to improve the detection of these types of acids. This method was shown to detect numerous end points in samples of bio-oil that were not detected by D664. These end points were attributed to carboxylic acids and phenolics based on the results of HPLC and GC-MS studies. Additional work has led to refinement of the method and it has been established that both carboxylic acids and phenolics can be determined accurately. Use of pH buffer calibration to determine half-neutralization potentials of acids in conjunction with the analysis of model compounds has allowed us to conclude that this titration method is suitable for the determination of total acid value of pyrolysis oil and can be used to differentiate and quantify weak acid species. The measurement of phenolics in bio-oil is subject to a relatively high limit of detection, which may limit the utility of titrimetric methodology for characterizing the acidic potential of pyrolysis oil and products.« less

Volcanic Aerosol Phosphorus, Chlorine, and Sulfur at Kilauea, Hawaii

DOE Office of Scientific and Technical Information (OSTI.GOV)

Darzi, M.; Winchester, J.W.

1982-12-20

Aerosol concentrations of P, Cl, S, and major soil-derived elements were measured sequentially at the Hawaiian Volcano Observatory (HVO) from March to September 1979, with 3.7-hour time resolution using a Nucleopore-filter sampler. The filters were analyzed by particle-induced X ray emission (PIXE). Comparison with diurnal variations in the air flow inferred from major soil elements, e.g., Fe, as well as measurements made previously at fumaroles near HVO, indicate that the P, C. and S may be attributed mainly to volcanic emissions from Kilauea. From April 23 to June 30, P was found with concentrations up to 1000 ng m/sup -3/;more » but before and after those dates, P was generally below the detection limit of 50--80 ng m/sup -3/. Cl and S were frequently found over the entire sampling period, also with concentrations up to 1000 ng m/sup -3/. However, when P was found, Cl was almost never detected simultaneously. The mutually exclusive occurrences of P and Cl suggest volatility release of HCl from aerosol particles by reaction with strong acid associated with P. If strong acidity is due to H/sub 2/SO/sub 4/, it is not well predicted by S, which may also include other sulfates or sulfur, since aerosol S concentrations are not well correlated with P or Cl. The behavior of these three elements suggests that the volcanic sources of P are more localized than those of Cl or S. It is significant that concentrations of aerosol P can be as high as aerosol Cl and S, all apparently of primary volcanic origin, indicating that volcanism may be an important, but hitherto unrecognized, process in the atmosphere goechemical cycling of phosphorus.« less

Application of direct-injection detector integrated with the multi-pumping flow system to chemiluminescence determination of the total polyphenol index.

PubMed

Nalewajko-Sieliwoniuk, Edyta; Iwanowicz, Magdalena; Kalinowski, Sławomir; Kojło, Anatol

2016-03-10

In this work, we present a novel chemiluminescence (CL) method based on direct-injection detector (DID) integrated with the multi-pumping flow system (MPFS) to chemiluminescence determination of the total polyphenol index. In this flow system, the sample and the reagents are injected directly into the cone-shaped detection cell placed in front of the photomultiplier window. Such construction of the detection chamber allows for fast measurement of the CL signal in stopped-flow conditions immediately after mixing the reagents. The proposed DID-CL-MPFS method is based on the chemiluminescence of nanocolloidal manganese(IV)-hexametaphosphate-ethanol system. The application of ethanol as a sensitizer, eliminated the use of carcinogenic formaldehyde. Under the optimized experimental conditions, the chemiluminescence intensities are proportional to the concentration of gallic acid in the range from 5 to 350 ng mL(-1). The DID-CL-MPFS method offers a number of advantages, including low limit of detection (0.80 ng mL(-1)), high precision (RSD = 3.3%) and high sample throughput (144 samples h(-1)) as well as low consumption of reagents, energy and low waste generation. The proposed method has been successfully applied to determine the total polyphenol index (expressed as gallic acid equivalent) in a variety of plant-derived food samples (wine, tea, coffee, fruit and vegetable juices, herbs, spices). Copyright © 2016 Elsevier B.V. All rights reserved.

Proximity hybridization-regulated chemiluminescence resonance energy transfer for homogeneous immunoassay.

PubMed

Liu, Mengmeng; Wu, Jie; Yang, Kaili; Zong, Chen; Lei, Jianping; Ju, Huangxian

2016-07-01

Chemiluminescence resonance energy transfer (CRET) and the proximity ligation assay have been widely used in design of sensors for the bioanalysis. Here, a wash-free and homogeneous strategy was proposed to detect carcino-embryonic antigen (CEA) based on proximity hybridization-regulated CRET. The Cy5 demonstrated strong chemiluminescence (CL) via the oxidation of TCPO in the presence of H2O2 and energy transfer between excited TCPO and Cy5. Graphene oxide (GO) as an excellent quencher was used to produce the "Signal off" mode that little CL emission was observed through CRET between GO and the Cy5-labelled DNA3. Once CEA was introduced, the target-induced proximity hybridization occurred to form a proximate complex, which inhibited the CRET by preventing GO from absorbing Cy5-labelled DNA3. Furthermore, taking advantage of nicking endonuclease Nt.BbvCI for in situ recycling, the signal could be further amplified for highly sensitive CL detection. Our results showed that this strategy enabled a specific response to CEA with a detection range of 5 orders of magnitude, along with a detection limit of 3.2pg mL(-1). Apart from its easy operation, high sensitivity and acceptable accuracy, the proposed method needed only 0.3μL of sample, indicating its great opportunity for commercial application. Copyright © 2016 Elsevier B.V. All rights reserved.

Detection of indomethacin by high-performance liquid chromatography with in situ electrogenerated Mn(III) chemiluminescence detection.

PubMed

Zhang, Yantu; Zhang, Zhujun; Qi, Guangcai; Sun, Yonghua; Wei, Yue; Ma, Hongyan

2007-01-23

The determination of indomethacin (INM) in pharmaceutical and biological samples by means of high-performance liquid chromatography (HPLC) with in situ electrogenerated Mn(III) chemiluminescence (CL) detection was proposed. The method was based on the direct CL reaction of INM and Mn(III), which was in situ electrogenerated by constant current electrolysis. The chromatographic separation was carried out on Nucleosil RP-C(18) column (250 mm x 4.6 mm; i.d., 5 microm; pore size, 100 A) at 20 degrees C. The mobile phase consisted of methanol:water:acetic acid=67:33:0.1 solution. At a flow rate of 1.0 mL min(-1), the total run time was 10 min. The effects of several parameters on the HPLC resolution and CL emission were studied systematically. Under the optimal conditions, a linear range from 0.01 to 10 microg mL(-1)(R(2)=0.9991), and a detection limit of 8 ng mL(-1) (signal-to-noise ratio=3) for INM were achieved. The relative standard deviations (R.S.D.) for 0.1 microg mL(-1) INM were 2.2% within a day (n=11) and 3.0% on 5 consecutive days (n=6), respectively. The recovery of INM from urine samples was more than 92%. The applicability of the method for the analysis of pharmaceutical and biological samples was examined.

Ultrasensitive determination of DNA sequences by flow injection chemiluminescence using silver ions as labels.

PubMed

Zheng, Lichun; Liu, Xiuhui; Zhou, Min; Ma, Yongjun; Wu, Guofan; Lu, Xiaoquan

2014-10-27

We presented a new strategy for ultrasensitive detection of DNA sequences based on the novel detection probe which was labeled with Ag(+) using metallothionein (MT) as a bridge. The assay relied on a sandwich-type DNA hybridization in which the DNA targets were first hybridized to the captured oligonucleotide probes immobilized on Fe3O4@Au composite magnetic nanoparticles (MNPs), and then the Ag(+)-modified detection probes were used to monitor the presence of the specific DNA targets. After being anchored on the hybrids, Ag(+) was released down through acidic treatment and sensitively determined by a coupling flow injection-chemiluminescent reaction system (Ag(+)-Mn(2+)-K2S2O8-H3PO4-luminol) (FI-CL). The experiment results showed that the CL intensities increased linearly with the concentrations of DNA targets in the range from 10 to 500 pmol L(-1) with a detection limit of 3.3 pmol L(-1). The high sensitivity in this work may be ascribed to the high molar ratio of Ag(+)-MT, the sensitive determination of Ag(+) by the coupling FI-CL reaction system and the perfect magnetic separation based on Fe3O4@Au composite MNPs. Moreover, the proposed strategy exhibited excellent selectivity against the mismatched DNA sequences and could be applied to real samples analysis. Copyright © 2014 Elsevier B.V. All rights reserved.

N-Hydroxysuccinimide as an effective chemiluminescence coreactant for highly selective and sensitive detection.

PubMed

Saqib, Muhammad; Li, Suping; Gao, Wenyue; Majeed, Saadat; Qi, Liming; Liu, Zhongyuan; Xu, Guobao

2016-12-01

The development of novel coreactants for chemiluminescence is very important to improve performance and widen its applications without using any other catalyst. N-Hydroxysuccinimide (NHS), a highly popular amine-reactive, activating, or protecting reagent in biochemical applications and organic synthesis, has been explored as an efficient and stable chemiluminescence coreactant for the first time. The chemiluminescence intensity of the newly developed luminol-NHS system is about 22 times higher than that of the traditional luminol-H 2 O 2 system. Chemiluminescence of this system is dramatically enhanced by Co 2+ . This new chemiluminescence system is then applied for the highly selective and ultrasensitive detection of Co 2+ with limit of detection (0.01 nM) better than those of several conventional analytical methods. This system also enables the efficient detection of luminol (LOD = 7 pM) and NHS (LOD = 3.0 μM) with excellent sensitivity. This chemiluminescence method was then also utilized to detect Co 2+ in tap water and blue silica gel with excellent recoveries in the range 99.20-103.07 %. This novel chemiluminescence system has several advantages, including simple, cost-effective, highly sensitive, selective, and wide linear range. We expect that this chemiluminescence system will be a promising candidate for chemical and biological sensing. Graphical Abstract Comparison of CL peak intensities of classical luminol-H 2 O 2 CL system and newly developed luminol-NHS CL system.

Determination of Sulfonamide Residues in Food by Capillary Zone Electrophoresis with On-Line Chemiluminescence Detection Based on an Ag(III) Complex.

PubMed

Dai, Tingting; Duan, Jie; Li, Xinghua; Xu, Xiangdong; Shi, Hongmei; Kang, Weijun

2017-06-16

The presence of sulfonamide (SA) residues in foods is largely due to the raising of animals with sulfonamide antibiotics added or polluted feedstuff. In this paper, a sensitive method was developed for the determination of the residues of three sulfonamides in animal-derived food; the SAs include sulfadimidine (SDD), sulfadiazine (SDZ), and sulfathiazole (STZ). The method is based on capillary zone electrophoresis (CE) with online chemiluminescence (CL) detection, using an Ag(III) complex as an oxidant. These SAs have an inhibiting effect on the Ag(III)-luminol CL reaction. The electrophoretic buffer is 12.0 mM sodium borate. Under a set of optimized conditions, the linear ranges for the detections were found to be 10.0-200 µg·mL -1 for SDD and SDZ, and 2.0-50.0 µg·mL -1 for STZ. The detection limits were 2.75, 3.14, and 0.65 µg·mL -1 for SDD, SDZ, and STZ, respectively. Relative standard deviations (RSD) for the peak heights were between 2.1% and 2.8% (n = 7). The proposed method was used in the analysis of the SAs in samples from pork meat, chicken meat, and milk, showing satisfactory detection results. A reaction mechanism was also proposed for the Ag(III)-luminol-SA CL reactions. The method has potential applications for the monitoring of residue levels of the three SAs in food, providing food safety data.

Development of a portable active long-path differential optical absorption spectroscopy system for volcanic gas measurements

USGS Publications Warehouse

Vita, Fabio; Kern, Christoph; Inguaggiato, Salvatore

2014-01-01

Active long-path differential optical absorption spectroscopy (LP-DOAS) has been an effective tool for measuring atmospheric trace gases for several decades. However, instruments were large, heavy and power-inefficient, making their application to remote environments extremely challenging. Recent developments in fibre-coupling telescope technology and the availability of ultraviolet light emitting diodes (UV-LEDS) have now allowed us to design and construct a lightweight, portable, low-power LP-DOAS instrument for use at remote locations and specifically for measuring degassing from active volcanic systems. The LP-DOAS was used to measure sulfur dioxide (SO2) emissions from La Fossa crater, Vulcano, Italy, where column densities of up to 1.2 × 1018 molec cm−2 (~ 500 ppmm) were detected along open paths of up to 400 m in total length. The instrument's SO2 detection limit was determined to be 2 × 1016 molec cm−2 (~ 8 ppmm), thereby making quantitative detection of even trace amounts of SO2 possible. The instrument is capable of measuring other volcanic volatile species as well. Though the spectral evaluation of the recorded data showed that chlorine monoxide (ClO) and carbon disulfide (CS2) were both below the instrument's detection limits during the experiment, the upper limits for the X / SO2 ratio (X = ClO, CS2) could be derived, and yielded 2 × 10−3 and 0.1, respectively. The robust design and versatility of the instrument make it a promising tool for monitoring of volcanic degassing and understanding processes in a range of volcanic systems.

A Field-expedient Method for Detection of Leptospirosis Causative Agents in Rodents

DTIC Science & Technology

2012-01-01

carboxytetramethylrhodamine (TAMRA)) (Roche Molecular Diagnostics, Pleasanton, California).24,25 Polymerase Chain Reaction. Wet reagent LPS PCR assay...City, Utah). Primers and probe were optimized with R.A.P.I.D. wet reagents and the optimum condition was 5 mmol/L MgCl2, 400 nmol/L primers, 100 nmol...for 20 seconds of combined annealing and primer extension. Linearity and Limit of Detection. The linearity of the LPS freeze-dried assay was

Layered double hydroxide-enhanced luminescence in a Fenton-like system for selective sensing of cobalt in Hela cells

NASA Astrophysics Data System (ADS)

Yu, Mei; Yuan, Zhiqin; Lu, Chao

2017-09-01

This work presented a facile and eco-friendly method for the determination of cobalt ions (Co(II)) in living cells based on layered double hydroxides (Mg-Al CO3-LDHs) enhanced chemiluminescence (CL) emission of a Co(II)-hydrogen peroxide-sodium hydroxide system. The enhanced CL emission was attributed to the large specific surface area of Mg-Al CO3-LDHs, which facilitates the generation of an excited-stated intermediate. The proposed method displayed high selectivity toward Co(II) over other metal ions. Under the optimal conditions, the increased CL intensity showed a linear response versus Co(II) concentration in the range of 5.0-1000 nM with a detection limit of 3.7 nM (S/N = 3). The relative standard deviation for nine repeated measurements of 100 nM Co(II) was 3.2%. Furthermore, the proposed method was successfully applied to detect Co(II) in living cell samples, and the results were agreed with those obtained by the standard ICP-MS method.

A new approach for bisphenol A detection employing fluorosurfactant-capped gold nanoparticle-amplified chemiluminescence from cobalt(II) and peroxymonocarbonate.

PubMed

Pan, Feng; Liu, Lin; Dong, Shichao; Lu, Chao

2014-07-15

In this work, we utilized the nonionic fluorosurfactant-capped gold nanoparticles (GNPs) as a novel chemiluminescence (CL) probe for the determination of trace bisphenol A. Bisphenol A can induce a sharp decrease in CL intensity from the GNP-Co(2+)-peroxymonocarbonate (HCO4(-)) system. Under the selected experimental conditions, a linear relationship was obtained between the CL intensity and the logarithm of concentration of bisphenol A in the range of 0.05-50 μM (R(2) = 0.9936), and the detection limit at a signal-to-noise ratio of 3 for bisphenol A was 10 nM. The applicability of the proposed method has been validated by determining bisphenol A in real polycarbonate samples with satisfactory results. The recoveries for bisphenol A in spiked samples were found to be between 94.4% and 105.0%. The relative standard deviation (RSD) for 12 repeated measurements of 0.5 μM bisphenol A was 2.2%. The proposed method described herein was simple, selective and obviated the need of extensive sample pretreatment. Copyright © 2014 Elsevier B.V. All rights reserved.

Gas chromatography coupled to tunable pulsed glow discharge time-of-flight mass spectrometry for environmental analysis.

PubMed

Solà-Vázquez, Auristela; Lara-Gonzalo, Azucena; Costa-Fernández, José M; Pereiro, Rosario; Sanz-Medel, Alfredo

2010-05-01

A tuneable microsecond pulsed direct current glow discharge (GD)-time-of-flight mass spectrometer MS(TOF) developed in our laboratory was coupled to a gas chromatograph (GC) to obtain sequential collection of the mass spectra, at different temporal regimes occurring in the GD pulses, during elution of the analytes. The capabilities of this set-up were explored using a mixture of volatile organic compounds of environmental concern: BrClCH, Cl(3)CH, Cl(4)C, BrCl(2)CH, Br(2)ClCH, Br(3)CH. The experimental parameters of the GC-pulsed GD-MS(TOF) prototype were optimized in order to separate appropriately and analyze the six selected organic compounds, and two GC carrier gases, helium and nitrogen, were evaluated. Mass spectra for all analytes were obtained in the prepeak, plateau and afterpeak temporal regimes of the pulsed GD. Results showed that helium offered the best elemental sensitivity, while nitrogen provided higher signal intensities for fragments and molecular peaks. The analytical performance characteristics were also worked out for each analyte. Absolute detection limits obtained were in the order of ng. In a second step, headspace solid phase microextraction (HS SPME), as sample preparation and preconcentration technique, was evaluated for the quantification of the compounds under study, in order to achieve the required analytical sensitivity for trihalomethanes European Union (EU) environmental legislation. The analytical figures of merit obtained using the proposed methodology showed rather good detection limits (between 2 and 13 microg L(-1) depending on the analyte). In fact, the developed methodology met the EU legislation requirements (the maximum level permitted in tap water for the "total trihalomethanes" is set at 100 microg L(-1)). Real analysis of drinking water and river water were successfully carried out. To our knowledge this is the first application of GC-pulsed GD-MS(TOF) for the analysis of real samples. Its ability to provide elemental, fragments and molecular information of the organic compounds is demonstrated.

Effects of environment on the release of Ni, Cr, Fe, and Co from new and recast Ni-Cr alloy.

PubMed

Oyar, Perihan; Can, Gülşen; Atakol, Orhan

2014-07-01

The addition of previously cast alloy to new alloy for economic reasons may increase the release of elements. The purpose of this study was to analyze the effects of the immersion period, immersion media, and addition of previously cast alloy to new alloy on the release of elements. Disk-shaped specimens were prepared from a Ni-Cr alloy (Ni: 61 wt%, Cr: 26 wt%, Mo: 11 wt%, Si: 1.5 wt%, Fe, Ce, Al, and Co <1 wt%) (Remanium CS; Dentaurum) with new alloy (group N) and 50% new/50% recast alloy (group R). After the immersion of the specimens in both NaCl (pH 4) and artificial saliva (pH 6.7) for 3, 7, 14, 30, and 60 days, the release of ions was determined by using atomic absorption spectrometry. Data were analyzed with a 3-way ANOVA (α=.001). The release of Ni was significantly affected by the immersion period, of Ni and Cr by the alloy and media (P<.01), and of Fe by the alloy (P<.01). Ion release from the recast alloy in artificial saliva was 109.71 for Ni, 6.49 for Cr, 223.22 for Fe, and 29.90 μg/L for Co. The release of Co in NaCl was below the detection limit in both groups. The release of Ni in NaCl and artificial saliva increased with the length of the immersion period in both groups. The release of Cr and Fe was higher in artificial saliva than in NaCl in group R, regardless of the immersion period. The release of Co in NaCl was below the detection limit in both groups. Copyright © 2014 The Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Optical sensing of hydrogen sulphate using rhodamine 6G hydrazide from aqueous medium

NASA Astrophysics Data System (ADS)

Upadhyay, Yachana; Bothra, Shilpa; Kumar, Rajender; Choi, Heung-Jin; Sahoo, Suban K.

2017-06-01

This communication reports the application of rhodamine 6G hydrazide (L) for the selective colorimetric and turn-on fluorescent sensing of hydrogen sulphate ions from aqueous medium. The ring opening of the colourless spirocyclic form of L was selectively triggered in the presence of HSO4- among the other tested anions (F-, Cl-, Br-, I-, AcO-, H2PO4-, NO3-, ClO4-, CN-, HO-, AsO33 - and SO42 -), which gives rise to a pink colour and strong fluorescence in the visible region. Sensor L showed a detection limit down to micromolar range without any interference from the other tested competitive anions. Sensor L was applied for the construction of two inputs (HO- and HSO4-) INHIBIT type molecular logic gate and naked-eye detection of HSO4- using test paper strips.

A real-time PCR diagnostic method for detection of Naegleria fowleri.

PubMed

Madarová, Lucia; Trnková, Katarína; Feiková, Sona; Klement, Cyril; Obernauerová, Margita

2010-09-01

Naegleria fowleri is a free-living amoeba that can cause primary amoebic meningoencephalitis (PAM). While, traditional methods for diagnosing PAM still rely on culture, more current laboratory diagnoses exist based on conventional PCR methods; however, only a few real-time PCR processes have been described as yet. Here, we describe a real-time PCR-based diagnostic method using hybridization fluorescent labelled probes, with a LightCycler instrument and accompanying software (Roche), targeting the Naegleria fowleriMp2Cl5 gene sequence. Using this method, no cross reactivity with other tested epidemiologically relevant prokaryotic and eukaryotic organisms was found. The reaction detection limit was 1 copy of the Mp2Cl5 DNA sequence. This assay could become useful in the rapid laboratory diagnostic assessment of the presence or absence of Naegleria fowleri. Copyright 2009 Elsevier Inc. All rights reserved.

Molecular imprinting-chemiluminescence determination of trimethoprim using trimethoprim-imprinted polymer as recognition material.

PubMed

He, Yunhua; Lu, Jiuru; Liu, Mei; Du, Jianxiu

2005-07-01

A new molecular imprinting-chemiluminescence method for the determination of trimethoprim was developed, in which trimethoprim-imprinted polymer was used as the molecular recognition material and the CL reaction of trimethoprim with potassium permanganate in acidic medium was used as the detection system. The CL intensity responds linearly to the concentration of trimethoprim within the 5.0 x 10(-8)-5.0 x 10(-6) g mL(-1) range (r= 0.9983) with a detection limit of 2 x 10(-8) g mL(-1). The relative standard deviation for the determination of 1.0 x 10(-7) g mL(-1) trimethoprim solutions is 4.8% (n= 9). The method has been applied to the determination of trimethoprim in pharmaceutical preparations and body fluids, and satisfactory results were obtained.

Chemiluminescence Resonance Energy Transfer-based Detection for Microchip Electrophoresis

PubMed Central

Huang, Yong; Shi, Ming; Liu, Rongjun

2010-01-01

Since the channels in micro- and nanofluidic devices are extremely small, a sensitive detection is required following microchip electrophoresis (MCE). This work describes a highly sensitive and yet universal detection scheme based on chemiluminescence resonance energy transfer (CRET) for MCE. It was found that an efficient CRET occurred between a luminol donor and a CdTe quantum dot (QD) acceptor in the luminol-NaBrO-QD system, and that it was sensitively suppressed by the presence of certain organic compounds of biological interest including biogenic amines and thiols, amino acids, organic acids, and steroids. These findings allowed developing sensitive MCE-CL assays for the tested compounds. The proposed MCE-CL methods showed desired analytical figures of merit such as a wide concentration range of linear response. Detection limits obtained were ~10−9 M for biogenic amines including dopamine and epinephrine, and ~ 10−8 M for biogenic thiols (e.g. glutathione and acetylcysteine), organic acids (i.e. ascorbic acid and uric acid), estrogens, and native amino acids. These were 10 to 1000 times more sensitive than those of previously reported MCE-based methods with chemiluminescence, electrochemical, or laser induced fluorescence detection for quantifying corresponding compounds. To evaluate the applicability of the present MCE-CL method for analyzing real biological samples, it was used to determine amino acids in individual human red blood cells. Nine amino acids including Lys, Ser, Ala, Glu, Trp, etc. were detected. The contents ranged from 3 to 31 amol /cell. The assay proved to be simple, quick, reproducible, and very sensitive. PMID:20121202

Simultaneous determination of five synthetic pyrethroid metabolites in urine by liquid chromatography-tandem mass spectrometry: application to 39 persons without known exposure to pyrethroids.

PubMed

Le Grand, R; Dulaurent, S; Gaulier, J M; Saint-Marcoux, F; Moesch, C; Lachâtre, G

2012-04-25

A sensitive and reliable method was developed and validated for the determination of five synthetic pyrethroid metabolites namely cis-Cl(2)CA, trans-Cl(2)CA, Br(2)CA, 3-PBA and 4-FPBA in human urine by liquid chromatography-tandem mass spectrometry. (2)D(6)-labelled trans-Cl(2)CA and (13)C(6)-labelled 3-PBA were used as internal standards. This method was based on a liquid-liquid extraction procedure in acidic conditions using hexane solvent with a basic purification, a chromatographic separation using a specific C18 column and mass spectrometric detection in the negative polarity. Suitable limits of detection (0.015μg/L for the five compounds) and quantification (from 0.020 to 0.030μg/L) were obtained for rendering the method usable for the biomonitoring of pyrethroids in the general population. The efficiency of the method was tested in 39 urine samples from French people without any known exposure to pyrethroids. At least three of the five metabolites were detected in each sample. The results of this study were compared to those obtained in previous ones and discussed. Copyright © 2011 Elsevier Ireland Ltd. All rights reserved.

A novel green analytical procedure for monitoring of azoxystrobin in water samples by a flow injection chemiluminescence method with off-line ultrasonic treatment.

PubMed

Yang, Xin-an; Zhang, Wang-bing

2013-01-01

A simple and green flow injection chemiluminescence (FI-CL) method for determination of the fungicide azoxystrobin was described for the first time. CL signal was generated when azoxystrobin was injected into a mixed stream of luminol and KMnO4 . The CL signal of azoxystrobin could be greatly improved when an off-line ultrasonic treatment was adopted. Meanwhile, the signal intensity increases with the analyte concentration proportionally. Several variables, such as the ultrasonic parameters, flow rate of reagents, concentrations of sodium hydroxide solution and CL reagents (potassium permanganate, luminol) were investigated, and the optimal CL conditions were obtained. Under optimal conditions, the linear range of 1-100 ng/mL for azoxystrobin was obtained and the detection limit (3σ) was determined as 0.13 ng/mL. The relative standard deviation was 1.5% for 10 consecutive measurements of 20 ng/mL azoxystrobin. The method has been applied to the determination of azoxystrobin residues in water samples. Copyright © 2012 John Wiley & Sons, Ltd.

Chemiluminescence microarrays in analytical chemistry: a critical review.

PubMed

Seidel, Michael; Niessner, Reinhard

2014-09-01

Multi-analyte immunoassays on microarrays and on multiplex DNA microarrays have been described for quantitative analysis of small organic molecules (e.g., antibiotics, drugs of abuse, small molecule toxins), proteins (e.g., antibodies or protein toxins), and microorganisms, viruses, and eukaryotic cells. In analytical chemistry, multi-analyte detection by use of analytical microarrays has become an innovative research topic because of the possibility of generating several sets of quantitative data for different analyte classes in a short time. Chemiluminescence (CL) microarrays are powerful tools for rapid multiplex analysis of complex matrices. A wide range of applications for CL microarrays is described in the literature dealing with analytical microarrays. The motivation for this review is to summarize the current state of CL-based analytical microarrays. Combining analysis of different compound classes on CL microarrays reduces analysis time, cost of reagents, and use of laboratory space. Applications are discussed, with examples from food safety, water safety, environmental monitoring, diagnostics, forensics, toxicology, and biosecurity. The potential and limitations of research on multiplex analysis by use of CL microarrays are discussed in this review.

Flow-injection chemiluminescence determination of ofloxacin and levofloxacin in pharmaceutical preparations and biological fluids.

PubMed

Sun, Hanwen; Li, Liqing; Chen, Xueyan

2006-08-01

A novel, rapid and sensitive analytical method is described for determination of ofloxacin and levofloxacin by enhanced chemiluminescence (CL) with flow-injection sampling. The method is based on the CL reaction of the Ce(IV)-Na2S2O4-ofloxacin/levofloxacin-H2SO2 system. The enhanced CL mechanism was developed and the optimum conditions for CL emission were investigated. The CL intensity was correlated linearly (r = 0.9988) with the concentration of ofloxacin (or levofloxacin) in the range of 1.0 x 10(-8) - 1.0 x 10(-7) g ml(-1) and 1.0 x 10(-7) - 6.0 x 10(-6) g ml(-1). The detection limit (S/N = 3) is 7 x 10(-9) g ml(-1). The relative standard derivation (RSD, n = 11) is 2.0% for ofloxacin at 4 x 10(-7) g ml(-1) and for levofloxacin at 6 x 10(-7) g ml(-1). This method has been successfully applied for the determination of ofloxacin and levofloxacin in pharmaceutical preparations and biological fluids with satisfactory results.

Using corona discharge-ion mobility spectrometry for detection of 2,4,6-Trichloroanisole.

PubMed

Lichvanová, Zuzana; Ilbeigi, Vahideh; Sabo, Martin; Tabrizchi, Mahmoud; Matejčík, Stefan

2014-09-01

In this work possible application of the corona discharge-ion mobility spectrometer (CD-IMS) for detection of 2,4,6-Trichloroanisole (TCA) has been investigated. We applied CD-IMS interfaced with orthogonal acceleration time of flight mass spectrometer (CD-IMS-oaTOF) to study the ion processes within the CD-IMS technique. The CD-IMS instrument was operated in two modes, (i) standard and (ii) reverse flow modes resulting in different chemical ionisation schemes by NO3(-)(HNO3)n (n=0,1,2) and O2(-)(H2O)n (n=0,1,2), respectively. The O2(-)(H2O)n ionisation was associated with formation of Cl(-) and (TCA-CH3)(-) ions from TCA. The NO3(-)(HNO3)n ionisation, resulted in formation of NO3(-)(HNO3)(TCA-Cl) adduct ions. Limit of detection (LOD) for TCA was determined in gas (100 ppb) and solid phases (150 ng). Copyright © 2014 Elsevier B.V. All rights reserved.

Enhanced chemiluminescent detection scheme for trace vapor sensing in pneumatically-tuned hollow core photonic bandgap fibers.

PubMed

Stolyarov, Alexander M; Gumennik, Alexander; McDaniel, William; Shapira, Ofer; Schell, Brent; Sorin, Fabien; Kuriki, Ken; Benoit, Gilles; Rose, Aimee; Joannopoulos, John D; Fink, Yoel

2012-05-21

We demonstrate an in-fiber gas phase chemical detection architecture in which a chemiluminescent (CL) reaction is spatially and spectrally matched to the core modes of hollow photonic bandgap (PBG) fibers in order to enhance detection efficiency. A peroxide-sensitive CL material is annularly shaped and centered within the fiber's hollow core, thereby increasing the overlap between the emission intensity and the intensity distribution of the low-loss fiber modes. This configuration improves the sensitivity by 0.9 dB/cm compared to coating the material directly on the inner fiber surface, where coupling to both higher loss core modes and cladding modes is enhanced. By integrating the former configuration with a custom-built optofluidic system designed for concomitant controlled vapor delivery and emission measurement, we achieve a limit-of-detection of 100 parts per billion (ppb) for hydrogen peroxide vapor. The PBG fibers are produced by a new fabrication method whereby external gas pressure is used as a control knob to actively tune the transmission bandgaps through the entire visible range during the thermal drawing process.

Label-free SERS study of galvanic replacement reaction on silver nanorod surface and its application to detect trace mercury ion

PubMed Central

Wang, Yaohui; Wen, Guiqing; Ye, Lingling; Liang, Aihui; Jiang, Zhiliang

2016-01-01

It is significant to explore a rapid and highly sensitive galvanic replacement reaction (GRR) surface enhanced Raman scattering (SERS) method for detection of trace mercury ions. This article was reported a new GRR SERS analytical platform for detecting Hg(II) with label-free molecular probe Victoria blue B (VBB). In HAc-NaCl-silver nanorod (AgNR) substrate, the molecular probe VBB exhibited a strong SERS peak at 1609 cm−1. Upon addition of Hg(II), the GRR occurred between the AgNR and Hg(II), and formed a weak SERS activity of Hg2Cl2 that deposited on the AgNR surfaces to decrease the SERS intensity at 1609 cm−1. The decreased SERS intensity was linear to Hg(II) concentration in the range of 1.25–125 nmol/L, with a detection limit of 0.2 nmol/L. The GRR was studied by SERS, transmission electron microscopy and other techniques, and the GRR mechanism was discussed. PMID:26792071

Chemical Analysis through CL-Detection Assisted by Periodate Oxidation

PubMed Central

Evmiridis, Nicholaos P.; Vlessidis, Athanasios G.; Thanasoulias, Nicholas C.

2007-01-01

The progress of the research work of the author and his colleagues on the field of CL-emission generated by pyrogallol oxidation and further application for the direct determination of periodate and indirect or direct determination of other compounds through flow-injection manifold/CL-detection set up is described. The instrumentation used for these studies was a simple flow-injection manifold that provides good reproducibility, coupled to a red sensitive photomultiplier that gives sensitive CL-detection. In addition, recent reports on studies and analytical methods based on CL-emission generated by periodate oxidation by other authors are included. PMID:17611611

An improved glycerol biosensor with an Au-FeS-NAD-glycerol-dehydrogenase anode.

PubMed

Mahadevan, Aishwarya; Fernando, Sandun

2017-06-15

An improved glycerol biosensor was developed via direct attachment of NAD + -glycerol dehydrogenase coenzyme-apoenzyme complex onto supporting gold electrodes, using novel inorganic iron (II) sulfide (FeS)-based single molecular wires. Sensing performance factors, i.e., sensitivity, a detection limit and response time of the FeS and conventional pyrroloquinoline quinone (PQQ)-based biosensor were evaluated by dynamic constant potential amperometry at 1.3V under non-buffered conditions. For glycerol concentrations ranging from 1 to 25mM, a 77% increase in sensitivity and a 53% decrease in detection limit were observed for the FeS-based biosensor when compared to the conventional PQQ-based counterpart. The electrochemical behavior of the FeS-based glycerol biosensor was analyzed at different concentrations of glycerol, accompanied by an investigation into the effects of applied potential and scan rate on the current response. Effects of enzyme stimulants ((NH 4 ) 2 SO 4 and MnCl 2 ·4H 2 O) concentrations and buffers/pH (potassium phosphate buffer pH 6-8, Tris buffer pH 8-10) on the current responses generated by the FeS-based glycerol biosensor were also studied. The optimal detection conditions were 0.03M (NH 4 ) 2 SO 4 and 0.3µm MnCl 2 ·4H 2 O in non-buffered aqueous electrolyte under stirring whereas under non-stirring, Tris buffer at pH 10 with 0.03M (NH 4 ) 2 SO 4 and 30µm MnCl 2 ·4H 2 O were found to be optimal detection conditions. Interference by glucose, fructose, ethanol, and acetic acid in glycerol detection was studied. The observations indicated a promising enhancement in glycerol detection using the novel FeS-based glycerol sensing electrode compared to the conventional PQQ-based one. These findings support the premise that FeS-based bioanodes are capable of biosensing glycerol successfully and may be applicable for other enzymatic biosensors. Copyright © 2016 Elsevier B.V. All rights reserved.

Flow injection chemiluminescence determination of naphazoline hydrochloride in pharmaceuticals.

PubMed

Iranifam, Mortaza; Sorouraddin, Mohammad H

2014-02-01

A simple and sensitive flow injection chemiluminescence (FI-CL) method was developed for the determination of naphazoline hydrochloride (NPZ). The method is based on the enhancing effect of NPZ on the weak CL signal from the reaction of KIO4 with H2 O2 . Experimental parameters that affected the CL signal, including the pH of the KIO4 solution, concentrations of KIO4 , H2 O2 and disodium-EDTA and flow rate were optimized. Under the optimum conditions, the increment of CL intensity was linearly proportional to the concentration of NPZ in the range 5.0 × 10(-6) to 70 × 10(-6) mol/L. The detection limit was 1.0 × 10(-6) mol/L and the relative standard deviation for 50 × 10(-6) mol/L NPZ solution was 2.8% (n = 11). In addition, a high throughput of 120 samples/h was achieved. The utility of this method was demonstrated by determining NPZ in pharmaceuticals. Copyright © 2013 John Wiley & Sons, Ltd.

Sensitive determination of 2-methoxyestradiol in pharmaceutical preparations and serum samples using flow injection chemiluminescence.

PubMed

Yao, Hanchun; Zhang, Min; Zeng, Wenyuan; Zeng, Xiaoying; Zhang, Zhenzhong

2014-05-01

A rapid and sensitive flow injection chemiluminescence (FI-CL) method is described for the determination of 2-methoxyestradiol (2ME) based on enhancement of the CL intensity from a potassium ferricyanide-calcein system in sodium hydroxide medium. The optimum conditions for the CL emission were investigated. Under optimized conditions, a linear calibration graph was obtained over the range 1.0 × 10(-8) to 1.0 × 10(-6) mol/L (r = 0.998) 2ME with a detection limit (3σ) of 5.4 × 10(-9) mol/L. The relative standard deviation (RSD) for 5.0 × 10(-7) mol/L 2ME was 1.7%. As a preliminary application, the proposed method was successfully applied to the determination of 2ME in injection solutions and serum samples. The possible CL mechanism was also proposed. Copyright © 2013 John Wiley & Sons, Ltd.

Streptavidin-functionalized capillary immune microreactor for highly efficient chemiluminescent immunoassay.

PubMed

Yang, Zhanjun; Zong, Chen; Ju, Huangxian; Yan, Feng

2011-11-07

A streptavidin functionalized capillary immune microreactor was designed for highly efficient flow-through chemiluminescent (CL) immunoassay. The functionalized capillary could be used as both a support for highly efficient immobilization of antibody and a flow cell for flow-through immunoassay. The functionalized inner wall and the capture process were characterized using scanning electron microscopy. Compared to conventional packed tube or thin-layer cell immunoreactor, the proposed microreactor showed remarkable properties such as lower cost, simpler fabrication, better practicality and wider dynamic range for fast CL immunoassay with good reproducibility and stability. Using α-fetoprotein as model analyte, the highly efficient CL flow-through immunoassay system showed a linear range of 3 orders of magnitude from 0.5 to 200 ng mL(-1) and a low detection limit of 0.1 ng mL(-1). The capillary immune microreactor could make up the shortcoming of conventional CL immunoreactors and provided a promising alternative for highly efficient flow-injection immunoassay. Copyright © 2011 Elsevier B.V. All rights reserved.

Permanganate-bromide-silver nanoparticles as a new chemiluminescence system and its application to captopril determination.

PubMed

Amjadi, Mohammad; Manzoori, Jamshid L; Hassanzadeh, Javad; Sorouraddin, Mohammad H

2013-10-15

A novel chemiluminescence (CL) system based on the oxidation of bromide by permanganate in sulfuric acid medium is introduced. The enhancing effect of silver nanoparticles (NPs), synthesized by chemical reduction method, on this reaction was studied. It was demonstrated that spherical silver nanoparticles with average size of 18 nm had a most remarkable catalytic effect on this reaction. CL emission wavelengths and UV-vis spectra were used to characterize the system and propose a possible mechanism. Furthermore, it was found that captopril inhibits the action of NPs and decreases the intensity of CL. Based on this phenomenon, a new CL method was developed for the determination of captopril in the 3.0 × 10(-10) to 1.0 × 10(-7) mol L(-1) concentration range with a detection limit (3s) of 0.12 nmol L(-1). The method was successfully applied to the determination of captopril in pharmaceutical formulations, human urine and serum samples. Copyright © 2013 Elsevier B.V. All rights reserved.

Multisyringe flow injection analysis hyphenated with liquid core waveguides for the development of cleaner spectroscopic analytical methods: improved determination of chloride in waters.

PubMed

Maya, Fernando; Estela, José Manuel; Cerdà, Víctor

2009-07-01

In this work, the hyphenation of the multisyringe flow injection analysis technique with a 100-cm-long pathlength liquid core waveguide has been accomplished. The Cl-/Hg(SCN)2/Fe3+ reaction system for the spectrophotometric determination of chloride (Cl(-)) in waters was used as chemical model. As a result, this classic analytical methodology has been improved, minimizing dramatically the consumption of reagents, in particular, that of the highly biotoxic chemical Hg(SCN)2. The proposed method features a linear dynamic range composed of two steps between (1) 0.2-2 and (2) 2-8 mg Cl- L(-1), thus extended applicability due to on-line sample dilution (up to 400 mg Cl- L(-1)). It also presents improved limits of detection and quantification of 0.06 and 0.20 mg Cl- L(-1), respectively. The coefficient of variation and the injection throughput were 1.3% (n = 10, 2 mg Cl- L(-1)) and 21 h(-1). Furthermore, a very low consumption of reagents per Cl- determination of 0.2 microg Hg(II) and 28 microg Fe3+ has been achieved. The method was successfully applied to the determination of Cl- in different types of water samples. Finally, the proposed system is critically compared from a green analytical chemistry point of view against other flow systems for the same purpose.

Recent advances and developments on integrating nanotechnology with chemiluminescence assays.

PubMed

Tiwari, Ashish; Dhoble, S J

2018-04-01

Chemiluminescence (CL) techniques are extensively utilized for detection of analytes due to their high sensitivity, rapidity and selectivity. With the advent of nanotechnology and incorporation of the nanoparticles in the CL system has revolutionized the assays due to their unique optical and mechanical properties. Several CL-based reactions have been developed where these nanoparticle based CL sensors have evolved as excellent prospects for sensing in various analytical applications. This review article addresses the nanoparticles based CL detection system that are recently developed, the mechanisms has been summarized and the role of luminophors have been discussed. This article critically analyzes the optimal conditions for the CL detection along with quantitative assessment of the analytes. We have included the use of semiconductor nanoparticles, metal nanoparticles, graphene based nanostructures, mesoporous nanospheres, layered double hydroxides, clays for CL detection. The scope and application of these nanoscale material based CL system in various branches of science and technology including chemistry, biomedical applications, pharmaceutics, food, environmental and toxicological applications has been critically summarized. Copyright © 2017 Elsevier B.V. All rights reserved.

Hybridization chain reaction-based instantaneous derivatization technology for chemiluminescence detection of specific DNA sequences.

PubMed

Wang, Xin; Lau, Choiwan; Kai, Masaaki; Lu, Jianzhong

2013-05-07

We propose here a new amplifying strategy that uses hybridization chain reaction (HCR) to detect specific sequences of DNA, where stable DNA monomers assemble on the magnetic beads only upon exposure to a target DNA. Briefly, in the HCR process, two complementary stable species of hairpins coexist in solution until the introduction of initiator reporter strands triggers a cascade of hybridization events that yield nicked double helices analogous to alternating copolymers. Moreover, a "sandwich-type" detection strategy is employed in our design. Magnetic beads, which are functionalized with capture DNA, are reacted with the target, and sandwiched with the above nicked double helices. Then, chemiluminescence (CL) detection proceeds via an instantaneous derivatization reaction between a specific CL reagent, 3,4,5-trimethoxylphenylglyoxal (TMPG), and the guanine nucleotides within the target DNA, reporter strands and DNA monomers for the generation of light. Our results clearly show that the amplification detection of specific sequences of DNA achieves a better performance (e.g. wide linear response range, low detection limit, and high specificity) as compared to the traditional sandwich type (capture/target/reporter) assays. Upon modification, the approach presented could be extended to detect other types of targets. We believe that this simple technique is promising for improving medical diagnosis and treatment.

Carbohydrate and alditol analysis by high-performance anion-exchange chromatography coupled with electrochemical detection at a cobalt-modified electrode.

PubMed

Casella, Innocenzo G; Contursi, Michela

2003-07-01

A cobalt oxyhydroxide film dispersed on a carbon electrode surface was characterized and proposed as an amperometric sensor for determination of alditols and carbohydrates in flowing streams. Complex mixtures of carbohydrates were separated by anion-exchange chromatography using a moderately alkaline solution as mobile phase. The cobalt modified electrode (GC-Co) was employed under a constant applied potential of 0.5 V (vs Ag/AgCl). Under these experimental conditions the detection limits (S/N=3) for all analyzed electroactive molecules ranged between 0.3 micromol L(-1) and 1.5 micromol L(-1) and the dynamic linear ranges spanned generally three orders of magnitude above the relevant detection limits. Analytical determinations of carbohydrates and alditols in red and white wines, are reported.

Platinum(II)-Oligonucleotide Coordination Based Aptasensor for Simple and Selective Detection of Platinum Compounds.

PubMed

Cai, Sheng; Tian, Xueke; Sun, Lianli; Hu, Haihong; Zheng, Shirui; Jiang, Huidi; Yu, Lushan; Zeng, Su

2015-10-20

Wide use of platinum-based chemotherapeutic regimens for the treatment for carcinoma calls for a simple and selective detection of platinum compound in biological samples. On the basis of the platinum(II)-base pair coordination, a novel type of aptameric platform for platinum detection has been introduced. This chemiluminescence (CL) aptasensor consists of a designed streptavidin (SA) aptamer sequence in which several base pairs were replaced by G-G mismatches. Only in the presence of platinum, coordination occurs between the platinum and G-G base pairs as opposed to the hydrogen-bonded G-C base pairs, which leads to SA aptamer sequence activation, resulting in their binding to SA coated magnetic beads. These Pt-DNA coordination events were monitored by a simple and direct luminol-peroxide CL reaction through horseradish peroxidase (HRP) catalysis with a strong chemiluminescence emission. The validated ranges of quantification were 0.12-240 μM with a limit of detection of 60 nM and selectivity over other metal ions. This assay was also successfully used in urine sample determination. It will be a promising candidate for the detection of platinum in biomedical and environmental samples.

Label-free as-grown double wall carbon nanotubes bundles for Salmonella typhimurium immunoassay.

PubMed

Punbusayakul, Niramol; Talapatra, Saikat; Ajayan, Pulickel M; Surareungchai, Werasak

2013-01-01

A label-free immunosensor from as-grown double wall carbon nanotubes (DW) bundles was developed for detecting Salmonella typhimurium. The immunosensor was fabricated by using the as-grown DW bundles as an electrode material with an anti-Salmonella impregnated on the surface. The immunosensor was electrochemically characterized by cyclic voltammetry. The working potential (100, 200, 300 and 400 mV vs. Ag/AgCl) and the anti-Salmonella concentration (10, 25, 50, 75, and 100 μg/mL) at the electrode were subsequently optimized. Then, chronoamperometry was used with the optimum potential of 100 mV vs. Ag/AgCl) and the optimum impregnated anti-Salmonella of 10 μg/mL to detect S. typhimurium cells (0-10(9) CFU/mL). The DW immunosensor exhibited a detection range of 10(2) to 10(7) CFU/mL for the bacteria with a limit of detection of 8.9 CFU/mL according to the IUPAC recommendation. The electrode also showed specificity to S. typhimurium but no current response to Escherichia coli. These findings suggest that the use of a label-free DW immunosensor is promising for detecting S. typhimurium.

New approach to the fast screening of plant oil samples for F-, Cl-, Br- and S-organic compounds on the trace level.

PubMed

Chivarzin, M E; Revelsky, I A; Nikoshina, A V; Buldyzkova, A N; Chepeliansky, D A; Revelsky, A I; Buriak, A K

2016-04-01

The fast method of the simultaneous determination of F(-), Cl(-), Br(-) and SO4(2-) anions in the deionized water on the trace level by ion chromatography using thorough cleaning of respective water containers, 10 μM NaHCO3 water solution as eluent, short Metrohm (50 × 4 mm) separation column and a large water volume injection is proposed. Calculated detection limits are 10(-9)-10(-8)% depending on the element. The method for the fast screening of plant oil samples for the total fluorine-, chlorine-, bromine- and sulfur-organic compounds content (calculated for the respective elements) on the trace level is developed. It is based on the high temperature combustion of oil sample in oxygen flow, absorption of the conversion products in deionized water and whole absorbate volume analysis for F(-), Cl(-), Br(-) and SO4(2-) anions, corresponding to the respective elements, using the developed method of these anions analysis by ion chromatography. The samples of soya, olive, sunflower and cotton seed oil were analyzed. The method detection limits (for 1mg sample) were 2 × 10(-6)%, 2 × 10(-6)%, 5 × 10(-6)% and 5 × 10(-6)% for fluorine, chlorine, bromine and sulfur, respectively. The relative standard deviation was ≤ 15%. The method gives the compressed information about the total content of all target and nontarget fluorine-, chlorine-, bromine- and sulfur-organic compounds in plant oils. Copyright © 2015. Published by Elsevier B.V.

A chemiluminescence biosensor based on the adsorption recognition function between Fe3O4@SiO2@GO polymers and DNA for ultrasensitive detection of DNA

NASA Astrophysics Data System (ADS)

Sun, Yuanling; Li, Jianbo; Wang, Yanhui; Ding, Chaofan; Lin, Yanna; Sun, Weiyan; Luo, Chuannan

2017-05-01

In this work, a chemiluminescence (CL) biosensor was prepared for ultrasensitive determination of deoxyribonucleic acid (DNA) based on the adsorption recognition function between core-shell Fe3O4@SiO2 - graphene oxide (Fe3O4@SiO2@GO) polymers and DNA. The Fe3O4@SiO2@GO polymers were composed by GO and magnetite nanoparticles. And the core-shell polymers were confirmed by Scanning Electron Microscope (SEM), X-Ray Powder Diffraction (XRD) and Fourier Transform Infrared (FTIR). Then Fe3O4@SiO2@GO was modified by DNA. Based on the principle of complementary base, Fe3O4@SiO2@GO-DNA was introduced to the CL system and the selectivity, sensitivity of DNA detection was significantly improved. The adsorption properties of Fe3O4@SiO2@GO to DNA were researched through the adsorption equilibrium, adsorption kinetic and thermodynamics. Under optimized CL conditions, DNA could be assayed with the linear concentration range of 5.0 × 10- 12-2.5 × 10- 11 mol/L. The detection limit was 1.7 × 10- 12 mol/L (3δ) and the relative standard deviation (RSD) was 3.1%. The biosensor was finally used for the determination of DNA in laboratory samples and recoveries ranged from 99% to 103%. The satisfactory results revealed the potential application of Fe3O4@SiO2@GO-DNA-CL biosensor in the diagnosis and the treatment of human genetic diseases.

Speciation of selenium and arsenic compounds by capillary electrophoresis with hydrodynamically modified electroosmotic flow and on-line reduction of selenium(VI) to selenium(IV) with hydride generation inductively coupled plasma mass spectrometric detection.

PubMed

Magnuson, M L; Creed, J T; Brockhoff, C A

1997-10-01

Capillary electrophoresis (CE) with hydride generation inductively coupled plasma mass spectrometry was used to determine four arsenicals and two selenium species. Selenate (SeVI) was reduced on-line to selenite (SeIV) by mixing the CE effluent with concentrated HCl. A microporous PTFE tube was used as a gas-liquid separator to eliminate the 40Ar37Cl and 40Ar35Cl interference from 77Se and 75As, respectively. The direction of the electroosmotic flow during CE was reversed with hydrodynamic pressure, which allowed increased freedom of buffer choice. For conventional pressure injection, method detection limits for SeIV and SeVI based on seven replicate injections were 10 and 24 pg, respectively. Recoveries of SeIV and SeVI in drinking water were measured.

Low-cost and reagent-free paper-based device to detect chloride ions in serum and sweat.

PubMed

Cinti, Stefano; Fiore, Luca; Massoud, Renato; Cortese, Claudio; Moscone, Danila; Palleschi, Giuseppe; Arduini, Fabiana

2018-03-01

The recent goal of sustainability in analytical chemistry has boosted the development of eco-designed analytical tools to deliver fast and cost-effective analysis with low economic and environmental impact. Due to the recent focus in sustainability, we report the use of low-cost filter paper as a sustainable material to print silver electrodes and to load reagents for a reagent-free electrochemical detection of chloride in biological samples, namely serum and sweat. The electrochemical detection of chloride ions was carried out by exploiting the reaction of the analyte (i.e. chloride) with the silver working electrode. During the oxidation wave in cyclic voltammetry the silver ions are produced, thus they react with chloride ions to form AgCl, while in the reduction wave, the following reaction occurs: AgCl + e - -->Ag + Cl - . These reactions at the electrode surface resulted in anodic/cathodic peaks directly proportional to the chloride ions in solution. Chloride ions were detected with the addition of only 10μL of the sample on the paper-based electrochemical cell, obtaining linearity up to 200mM with a detection limit equal to 1mM and relative standard deviation lower than 10%. The accuracy of the sensor was evaluated in serum and sweat samples, with percentage recoveries between 93 ± 10 and 108 ± 8%. Moreover, the results achieved with the paper-based device were positively compared with those obtained by using the gold standard method (Ion Selective Electrode) adopted in routine clinical analyses. Copyright © 2017 Elsevier B.V. All rights reserved.

Determination of Sulfonamide Residues in Food by Capillary Zone Electrophoresis with On-Line Chemiluminescence Detection Based on an Ag(III) Complex

PubMed Central

Dai, Tingting; Duan, Jie; Li, Xinghua; Xu, Xiangdong; Shi, Hongmei; Kang, Weijun

2017-01-01

The presence of sulfonamide (SA) residues in foods is largely due to the raising of animals with sulfonamide antibiotics added or polluted feedstuff. In this paper, a sensitive method was developed for the determination of the residues of three sulfonamides in animal-derived food; the SAs include sulfadimidine (SDD), sulfadiazine (SDZ), and sulfathiazole (STZ). The method is based on capillary zone electrophoresis (CE) with online chemiluminescence (CL) detection, using an Ag(III) complex as an oxidant. These SAs have an inhibiting effect on the Ag(III)–luminol CL reaction. The electrophoretic buffer is 12.0 mM sodium borate. Under a set of optimized conditions, the linear ranges for the detections were found to be 10.0–200 µg·mL−1 for SDD and SDZ, and 2.0–50.0 µg·mL−1 for STZ. The detection limits were 2.75, 3.14, and 0.65 µg·mL−1 for SDD, SDZ, and STZ, respectively. Relative standard deviations (RSD) for the peak heights were between 2.1% and 2.8% (n = 7). The proposed method was used in the analysis of the SAs in samples from pork meat, chicken meat, and milk, showing satisfactory detection results. A reaction mechanism was also proposed for the Ag(III)–luminol–SA CL reactions. The method has potential applications for the monitoring of residue levels of the three SAs in food, providing food safety data. PMID:28621728

Development of an Electrochemical Immunosensor for Fumonisins Detection in Foods

PubMed Central

Kadir, Mohamad Kamal Abdul; Tothill, Ibtisam E.

2010-01-01

An electrochemical affinity sensor for the determination of fumonisins mycotoxins (Fms) using monoclonal antibody modified screen-printed gold electrode with carbon counter and silver-silver chloride pseudo-reference electrode is reported in this work. A direct competitive enzyme-linked immunosorbent assay (ELISA) was initially developed, exhibiting a detection limit of 100 µg·L-1 for fumonisins. This was then transferred to the surface of a bare gold screen-printed electrode (SPGE) and detection was performed by chronoamperometry, monitoring the reaction of 3,3’,5,5’-Tetramethylbenzidine dihydrochloride (TMB) and hydrogen peroxide (H2O2) catalysed by HRP at −100 mV potential vs. onboard Ag-AgCl pseudo-reference electrode. The immunosensor exhibited detection limit of 5 µg·L−1 fumonisins with a dynamic range from 1 µg·L−1–1000 µg·L−1. The sensor also performed well in extracted corn samples. PMID:22069591

Efficacy of chlorine dioxide on Escherichia coli inactivation during pilot-scale fresh-cut lettuce processing.

PubMed

Banach, J L; van Overbeek, L S; Nierop Groot, M N; van der Zouwen, P S; van der Fels-Klerx, H J

2018-03-23

Controlling water quality is critical in preventing cross-contamination during fresh produce washing. Process wash water (PWW) quality can be controlled by implementing chemical disinfection strategies. The aim of this study was to evaluate the pilot-scale efficacy of chlorine dioxide (ClO 2 ) during processing on the reduction of Escherichia coli in the PWW and on processed fresh-cut 'Lollo Rossa' lettuce. The objective was to have a residual target concentration of either 5 or 3 mg/L ClO 2 in the washing tank (3.5 m 3 ) before and during 800 kg of lettuce processing (90 min). After 90 min., a nonpathogenic, non-Extended Spectrum Beta-Lactamase (ESBL) E. coli inoculum from an overnight culture broth (37 °C) was added to the tank resulting in an approximate final level of 10 6  CFU/mL. PWW and lettuce samples for microbiological and chemical analyses were taken before and after the input and supply halted. ClO 2 concentrations quickly decreased after ClO 2 input halted, yet a residual concentration of ≥2.5 mg/L and ≥2.1 mg/L ClO 2 , respectively for 5 and 3 mg/L pilots, was present 12 min after the supply halted. No detectable levels of E. coli (limit of detection 5 log) were determined in the water within 1 min after E. coli was added to the ClO 2 containing wash water. Results demonstrated that ClO 2 use at the semi-commercial pilot scale was able to reduce the E. coli peak contamination in the PWW. After storage (5 days, 4 °C), background microbial communities (i.e., fluorescent Pseudomonads and total heterotrophic bacteria) grew out on lettuce. Overall, ClO 2 decreased the potential for cross-contamination between batches compared to when no sanitizer was used. Chlorate levels of the lettuce sampled before entering the wash water ranged from 7.3-11.6 μg/kg. The chlorate levels of the lettuce sampled after being washed in the ClO 2 containing wash water, as well as after rinsing and centrifugation, ranged from 22.8-60.4 μg/kg; chlorite levels ranged from 1.3-1.6 mg/kg, while perchlorate levels were below the limit of quantification (LOQ, <5 ng/g). In this study, we report the semi-commercial pilot-scale evaluation of ClO 2 , for its ability to maintain the PWW quality and to prevent cross-contamination in the washing tank during fresh-cut lettuce processing. Furthermore, we provide quantitative values of ClO 2 disinfection by-products chlorate and chlorite as well as of perchlorate from PWW and/or lettuce samples. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

A reliable combination method to identification and typing of epidemic and endemic clones among clinical isolates of Acinetobacter baumannii.

PubMed

Piran, Arezoo; Shahcheraghi, Fereshteh; Solgi, Hamid; Rohani, Mahdi; Badmasti, Farzad

2017-10-01

The multi-drug resistant (MDR) Acinetobacter baumannii as an important nosocomial pathogen has emerged a global health concern in recent years. In this study, we applied three easier, faster, and cost-effective methods including PCR-based open reading frames (ORFs) typing, sequence typing of bla OXA-51-like and RAPD-PCR method to rapid typing of A. baumannii strains. Taken together in the present study the results of ORFs typing, PCR-sequencing of bla OXA-51-like genes and MLST sequence typing revealed there was a high prevalence (62%, 35/57) of ST2 as international and successful clone which detected among clinical isolates of multi-drug resistant A. baumannii with ORF pattern B and bla OXA-66 gene. Only 7% (4/57) of MDR isolates belonged to ST1 with ORF pattern A and bla OXA-69 gene. Interestingly, we detected singleton ST513 (32%, 18/57) that encoded bla OXA-90 and showed the ORF pattern H as previously isolated in Middle East. Moreover, our data showed RAPD-PCR method can detect divergent strains of the STs. The Cl-1, Cl-2, Cl-3, Cl-4, Cl-10, Cl-11, Cl-12, Cl-13 and Cl-14 belonged to ST2. While the Cl-6, Cl-7, Cl-8 and Cl-9 belonged to ST513. Only Cl-5 belonged to ST1. It seems that the combination of these methods have more discriminatory than any method separately and could be effectively applied to rapid detection of the clonal complex (CC) of A. baumannii strains without performing of MLST or PFGE. Copyright © 2017 Elsevier B.V. All rights reserved.

Flow injection chemiluminescence determination of the total phenolics levels in plant-derived beverages using soluble manganese(IV).

PubMed

Nalewajko-Sieliwoniuk, Edyta; Tarasewicz, Iwona; Kojło, Anatol

2010-05-23

This study established a flow injection (FI) methodology for the determination of the total phenolic content in plant-derived beverages based on soluble manganese(IV) chemiluminescence (CL) detection. It was found that mixing polyphenols with acidic soluble manganese(IV) in the presence of formaldehyde evoked chemiluminescence. Based on this finding, a new FI-CL method was developed for the estimation of the total content of phenolic compounds (expressed as milligrams of gallic acid equivalent per litre of drink) in a variety of wine, tea and fruit juice samples. The proposed method is sensitive with a detection limit of 0.02 ng mL(-1) (gallic acid), offers a wide linear dynamic range (0.5-400 ng mL(-1)) and high sample throughput (247 samples h(-1)). The relative standard deviation for 15 measurements was 3.8% for 2 ng mL(-1) and 0.45% for 10 ng mL(-1) of gallic acid. Analysis of 36 different samples showed that the results obtained by the proposed FI-CL method correlate highly with those obtained by spectrophotometric methods commonly used for the evaluation of the total phenolic/antioxidant level. However, the FI-CL method was found to be far simpler, more rapid and selective, with almost no interference from non-phenolic components of the samples examined. Copyright 2010 Elsevier B.V. All rights reserved.

A simple and sensitive flow injection method based on the catalytic activity of CdS quantum dots in an acidic permanganate chemiluminescence system for determination of formaldehyde in water and wastewater.

PubMed

Khataee, Alireza; Lotfi, Roya; Hasanzadeh, Aliyeh; Iranifam, Mortaza

2016-04-01

A simple and sensitive flow injection chemiluminescence (CL) method in which CdS quantum dots (QDs) enhanced the CL intensity of a KMnO4-formaldehyde (HCHO) reaction was offered for the determination of HCHO. This CL system was based on the catalytic activity of CdS QDs and their participation in the CL resonance energy transfer (CRET) phenomenon. A possible mechanism for the supplied CL system was proposed using the kinetic curves of the CL systems and the spectra of CL, photoluminescence (PL) and ultraviolet-visible (UV-Vis). The emanated CL intensity of the KMnO4-CdS QDs system was amplified in the presence of a trace level of HCHO. Based on this enhancement effect, a simple and sensitive flow injection CL method was suggested for the determination of HCHO concentration in environmental water and wastewater samples. Under selected optimized experimental conditions, the increased CL intensity was proportional to the HCHO concentration in the range of 0.03-4.5 μg L(-1) and 4.5-10.0 μg L(-1). The detection limits (3σ) were 0.0003 μg L(-1) and 1.2 μg L(-1). The relative standard deviations (RSD%) for eleven replicate determinations of 4.0 μg L(-1) HCHO were 2.2%. Furthermore, the feasibility of the developed method was investigated via the determination of HCHO concentration in environmental water and wastewater samples.

A novel on-line gold nanoparticle-catalyzed luminol chemiluminescence detector for high-performance liquid chromatography.

PubMed

Zhang, Qun Lin; Wu, Liang; Lv, Chen; Zhang, Xiao Yue

2012-06-15

A novel on-line gold nanoparticle-catalyzed luminol-H(2)O(2) chemiluminescence (CL) detector for high-performance liquid chromatography (HPLC) was established, in which gold nanoparticles were produced by the on-line reaction of H(2)O(2), NaHCO(3)-Na(2)CO(3) (buffer solution of luminol), and HAuCl(4). Eight phenolic compounds (gallic acid, protocatechuic acid, protocatechuic aldehyde, 2,5-dihydroxybenzoic acid, caffeic acid, 2,3-dihydroxybenzoic acid, (+)-catechin, and (-)-epicatechin) were chosen as the model compounds. Every separated phenolic compound in the column eluent strongly enhanced the CL signal of on-line gold nanoparticle-catalyzed luminol system. The CL and UV-visible absorption spectra and transmission electron microscopy studies were carried out, and the CL enhancement mechanism was ascribed to that the presence of phenolic compound promoted the on-line formation of 38-nm-diameter gold nanoparticles, which better catalyzed the luminol-H(2)O(2) CL reaction. The effects of methanol and phosphoric acid in the proposed HPLC configuration were performed by two gradient elution programs, and the baseline profile revealed that on-line gold nanoparticle-catalyzed luminol-H(2)O(2) CL detector had better compatibility than 38 nm gold colloids-luminol-H(2)O(2) CL detector. The proposed CL detector exhibits excellent analytical performance with the low detection limit (S/N=3) of 0.53-0.97 ng/mL (10.6-19.4 pg) phenolic compounds, and offers a new strategy for developing on-line nanoparticle-catalyzed CL detector for HPLC with sensitive analysis. Copyright © 2012 Elsevier B.V. All rights reserved.

Fluorination of Boron-Doped Diamond Film Electrodes for Minimization of Perchlorate Formation.

PubMed

Gayen, Pralay; Chaplin, Brian P

2017-08-23

This research investigated the effects of surface fluorination on both rates of organic compound oxidation (phenol and terephthalic acid (TA)) and ClO 4 - formation at boron-doped diamond (BDD) film anodes at 22 °C. Different fluorination methods (i.e., electrochemical oxidation with perfluorooctanoic acid (PFOA), radio frequency plasma, and silanization) were used to incorporate fluorinated moieties on the BDD surface, which was confirmed by X-ray photoelectron spectroscopy (XPS). The silanization method was found to be the most effective fluorination method using a 1H,1H,2H,2H-perfluorodecyltrichlorosilane precursor to form a self-assembled monolayer (SAM) on the oxygenated BDD surface. The ClO 4 - formation decreased from rates of 0.45 ± 0.03 mmol m -2 min -1 during 1 mM NaClO 3 oxidation and 0.28 ± 0.01 mmol m -2 min -1 during 10 mM NaCl oxidation on the BDD electrode to below detectable levels (<0.12 μmoles m -2 min -1 ) for the BDD electrode functionalized by a 1H,1H,2H,2H-perfluorodecyltrichlorosilane SAM. These decreases in rates corresponded to 99.94 and 99.85% decreases in selectivity for ClO 4 - formation during the electrolysis of 10 mM NaCl and 1 mM NaClO 3 electrolytes, respectively. By contrast, the oxidation rates of phenol were reduced by only 16.3% in the NaCl electrolyte and 61% in a nonreactive 0.1 M KH 2 PO 4 electrolyte. Cyclic voltammetry with Fe(CN) 6 3-/4- and Fe 3+/2+ redox couples indicated that the long fluorinated chains created a blocking layer on the BDD surface that inhibited charge transfer via steric hindrance and hydrophobic effects. The surface coverages and thicknesses of the fluorinated films controlled the charge transfer rates, which was confirmed by estimates of film thicknesses using XPS and density functional theory simulations. The aliphatic silanized electrode also showed very high stability during OH • production. Perchlorate formation rates were below the detection limit (<0.12 μmoles m -2 min -1 ) for up to 10 consecutive NaClO 3 oxidation experiments.

Ultra-sensitive chemiluminescence imaging DNA hybridization method in the detection of mosquito-borne viruses and parasites.

PubMed

Zhang, Yingjie; Liu, Qiqi; Zhou, Biao; Wang, Xiaobo; Chen, Suhong; Wang, Shengqi

2017-01-25

Mosquito-borne viruses (MBVs) and parasites (MBPs) are transmitted through hematophagous arthropods-mosquitoes to homoiothermous vertebrates. This study aims at developing a detection method to monitor the spread of mosquito-borne diseases to new areas and diagnose the infections caused by MBVs and MBPs. In this assay, an ultra-sensitive chemiluminescence (CL) detection method was developed and used to simultaneously detect 19 common MBVs and MBPs. In vitro transcript RNA, virus-like particles (VLPs), and plasmids were established as positive or limit of detection (LOD) reference materials. MBVs and MBPs could be genotyped with high sensitivity and specificity. The cut-off values of probes were calculated. The absolute LODs of this strategy to detect serially diluted in vitro transcribed RNAs of MBVs and serially diluted plasmids of MBPs were 10 2 -10 3 copies/μl and 10 1 -10 2 copies/μl, respectively. Further, the LOD of detecting a strain of pre-quantified JEV was 10 1.8 -10 0.8 PFU/ml, fitted well in a linear regression model (coefficient of determination = 0.9678). Ultra-sensitive CL imaging DNA hybridization was developed and could simultaneously detect various MBVs and MBPs. The method described here has the potential to provide considerable labor savings due to its ability to screen for 19 mosquito-borne pathogens simultaneously.

Determination Co 2+ in vitamin B 12 based on enhancement of 2-(4-substituted-phenyl)-4,5-di(2-furyl) imidazole and H 2O 2 chemiluminescence reaction

NASA Astrophysics Data System (ADS)

Han, Lu; Zhang, Yumin; Kang, Jing; Tang, Jieli; Zhang, Yihua

2011-11-01

In this paper, three kinds of imidazole derivatives, 2-(4-methylphenyl)-4,5-di(2-furyl) imidazole (MDFI), 2-(4-nitrophenyl)-4,5-di(2-furyl) imidazole (NDFI), and 2-(4-tert-butylphenyl)-4,5-di(2-furyl) imidazole (t-BDFI) were synthesized. In an alkaline medium, the chemiluminescence (CL) reaction of imidazole derivatives with H 2O 2 has been investigated. It was also found that MDFI/H 2O 2 and t-BDFI/H 2O 2 systems gave strong CL. When Co 2+ was added into the two CL systems, the CL intensity was remarkably enhanced. In the optimum conditions, the CL intensity is linearly related to the logarithm of concentration of Co 2+. The linear ranges are 5 × 10 -9-2.5 × 10 -7 mol/L for MDFI/H 2O 2 system and 5 × 10 -9-2.5 × 10 -7 mol/L for t-BDFI/H 2O 2 system, and the corresponding detection limits are 1.2 × 10 -9 mol/L and 1.1 × 10 -9 mol/L, respectively. The method was applied to the determination of Co 2+ in vitamin B 12 injection. Furthermore, the CL mechanism was also discussed.

Is 3D MPRAGE better than the combination DIR/PSIR for cortical lesion detection at 3T MRI?

PubMed

Nelson, Flavia; Poonawalla, Aziz; Datta, Sushmita; Wolinsky, Jerry; Narayana, Ponnada

2014-03-01

Based on the application of newer magnetic resonance imaging (MRI) acquisition sequences, the detection of cortical lesions (CL) in multiple sclerosis (MS) has significantly improved. Double inversion recovery (DIR) at 3T has increased the detection sensitivity and classification specificity when combined with phase sensitive inversion recovery (PSIR). Previous findings with 3D magnetization prepared rapid acquisition with gradient echo (MPRAGE) sequences, showed improved classification specificity of purely intracortical (IC) and mixed (MX) lesions, compared to the classification based on DIR/PSIR. Direct comparison between the detection of CL by 3D MPRAGE and by DIR/PSIR at 3T has not been evaluated. Eleven subjects were imaged on a 3T magnet. DIR/PSIR and 3D MPRAGE images were reviewed independently. Each image set was reviewed twice; only lesions detected on both sessions were scored. Review time per scan was ~5min for DIR/PSIR and ~15min for 3D MPRAGE. We identified 141 CL (62 IC+79 MX) based on DIR/PSIR images vs. 93 (38 IC+55 MX) based on MPRAGE from all eleven patients. MPRAGE under-detected the number of CL in seven cases and over-detected the number of CL in three, only one case had the same number of CL on both sets of images. Combination DIR/PSIR at 3T is superior to 3D MPRAGE for detection of cortical gray matter lesions in MS. The contrast-to-noise ratio of CL appears to be inferior on the MPRAGE images relative to DIR/PSIR. © 2013 Published by Elsevier B.V.

High-Altitude Aircraft and Balloon-Borne Observations of OH, HO2, ClO, BrO, NO2, ClONO2, ClOOCl, H2O, and O3 in Earth's Stratosphere

NASA Technical Reports Server (NTRS)

Anderson, James G.

1999-01-01

Using observations from balloon-borne instruments and aircraft-borne instruments the investigation arrived at the following developments.: (1) Determination of the dominant catalytic cycles that destroy ozone in the lower stratosphere; (2) The partial derivatives of the rate limiting steps are observables in the lower stratosphere; (3) Recognition that the "Low NOx" condition is the regime that holds the greatest potential for misjudgement of Ozone loss rates; (4) Mapping of the Bromine radical contribution to the ozone destruction rate in the lower stratosphere; (5) Observation of OH, HO2 and ClO in the plume of the Concorde SST in the stratosphere; (6) Determination of the diurnal behavior of OH in the lower stratosphere; (7) Observed OH and H02 in the Troposphere and the interrelationship between Ozone and OH, HO2, CO and NO; (8) Analysis of the Catalytic Production of Ozone and Reactions that Couple OH and H02 in the Troposphere; (9) The continuing development of the understanding of the Tropopause temperatures, water vapor mixing ratios, and vertical advection and the mixing in of mid-latitude air; (10) Performed Multiple Tracer Analyses as a diagnostic of water vapor intrusion into the "Middle World" (i.e., the lowermost stratsophere); (11) Flight testing of a new instrument for the In Situ detection of ClON02 from the ER-2; (12) Laser induced fluorescence detection of NO2. There is included an in depth discussion of each of these developments and observations.

The Effect of Gamma Radiation on Mars Mineral Matrices: Implications for Perchlorate Formation on Mars

NASA Astrophysics Data System (ADS)

Fox, A. C.; Eigenbrode, J. L.; Pavlov, A.; Lewis, J.

2017-12-01

Observations by the Phoenix Wet Chemistry Lab of the Martian surface indicate the presence of perchlorate in high concentrations. Additional observations by the Sample Analysis at Mars and the Viking Landers indirectly support the presence of perchlorate at other localities on Mars. The evidence for perchlorate at several localities on Mars coupled with its detection in Martian meteorite EETA79001 suggests that perchlorate is present globally on Mars. The presence of perchlorate on Mars further complicates the search for organic molecules indicative of past life. While perchlorate is kinetically limited in Martian conditions, the intermediate species associated with its formation or decomposition, such as chlorate or chlorite, could oxidize Martian organic species. As a result, it is vital to understand the mechanism of perchlorate formation on Mars in order to determine its role in the degradation of organics. Here, we explore an alternate mechanism of formation of perchlorate by bombarding Cl-salts and Mars-relevant mineral mixtures with gamma radiation both with and without the presence of liquid water, under vacuum. Previous work has shown that OClO can form from both UV radiation and energetic electrons bombardment of Cl-ices or Cl-salts, which then reacts with either OH- or O-radicals to produce perchlorate. Past research has suggested that liquid water or ice is the source of these hydroxyl and oxygen radicals, which limits the location of perchlorate formation on Mars. We demonstrate that trace amounts of perchlorate are potentially formed in samples containing silica dioxide or iron oxide and Cl-salts both with and without liquid water. Perchlorate was also detected in a portion of samples that were not irradiated, suggesting possible contamination. We did not detect perchlorate in samples that contained sulfate minerals. If perchlorate was formed without liquid water, it is possible that oxide minerals could be a potential source of oxygen radicals required to produce perchlorate. This finding could help explain the global presence of perchlorate and has implications for the survival of organic molecules on Mars.

Molecularly imprinted polymer based on chemiluminescence imaging for the chiral recognition of dansyl-phenylalanine.

PubMed

Wang, Li; Zhang, Zhujun; Huang, Lianggao

2008-03-01

A new molecularly imprinted polymer (MIP)-chemiluminescence (CL) imaging detection approach towards chiral recognition of dansyl-phenylalanine (Phe) is presented. The polymer microspheres were synthesized using precipitation polymerization with dansyl-L-Phe as template. Polymer microspheres were immobilized in microtiter plates (96 wells) using poly(vinyl alcohol) (PVA) as glue. The analyte was selectively adsorbed on the MIP microspheres. After washing, the bound fraction was quantified based on peroxyoxalate chemiluminescence (PO-CL) analysis. In the presence of dansyl-Phe, bis(2,4,6-trichlorophenyl)oxalate (TCPO) reacted with hydrogen peroxide (H2O2) to emit chemiluminescence. The signal was detected and quantified with a highly sensitive cooled charge-coupled device (CCD). Influencing factors were investigated and optimized in detail. Control experiments using capillary electrophoresis showed that there was no significant difference between the proposed method and the control method at a confidence level of 95%. The method can perform 96 independent measurements simultaneously in 30 min and the limits of detection (LODs) for dansyl-L-Phe and dansyl-D-Phe were 0.025 micromol L(-1) and 0.075 micromol L(-1) (3sigma), respectively. The relative standard deviation (RSD) for 11 parallel measurements of dansyl-L-Phe (0.78 micromol L(-1)) was 8%. The results show that MIP-based CL imaging can become a useful analytical technology for quick chiral recognition.

Kinetic response study in chemiresistive gas sensor based on carbon nanotube surface functionalized with substituted phthalocyanines

NASA Astrophysics Data System (ADS)

Sharma, Anshul Kumar; Kumar, Pankaj; Saini, Rajan; Bedi, R. K.; Mahajan, Aman

2016-05-01

A kind of hybrid material is prepared by functionalizing multi-wall carbon nanotubes (MWCNTs-COOH) with substituted copper phthalocyanine and the formation of CuPcOC8/MWCNTs-COOH hybrid is confirmed by scanning electron microscopy and transmission electron microscopy. The results indicated that on the surface of nanotubes substituted CuPcOC8 derivatives has been successfully anchored through π-π stacking interaction. The gas sensing application of the fabricated hybrid material is tested upon exposure to different hazardous species, specifically NO2, NO, Cl2 and NH3 at operating temperature of 150˚C. It has been demonstrated that for Cl2 minimum detection limit of CuPcOC8/MWCNTs-COOH hybrid is 100 ppb. The response of hybrid sensor is found to be increased with increase in the concentration of Cl2.

Post-chemiluminescence determination of chloramphenicol based on luminol-potassium periodate system.

PubMed

Yang, Xiao Feng; Li, Nian Bing; Luo, Hong Qun

2012-01-01

A post-chemiluminescence (PCL) phenomenon was observed when chloramphenicol was injected into a mixture of luminol and potassium periodate after the chemiluminescence (CL) reaction of luminol-potassium periodate had finished. The possible reaction mechanism was proposed based on studies of the CL kinetic characteristics, the CL spectra, the fluorescence spectra and the UV-vis absorption spectra of the related substances. Based on the PCL reaction, a rapid and sensitive method for the determination of chloramphenicol was established. The linear response range was 6.0 × 10(-7) -1.0 × 10(-5) mol/L, with a correlation coefficient of 0.9986. The relative standard deviation (RSD) for 5.0 × 10(-6) mol/L chloramphenicol was 2.3% (n = 11). The detection limit was 1.6 × 10(-7) mol/L. The method has been applied to the determination of chloramphenicol in pharmaceutical samples with satisfactory results. Copyright © 2011 John Wiley & Sons, Ltd.

Kinetic response study in chemiresistive gas sensor based on carbon nanotube surface functionalized with substituted phthalocyanines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharma, Anshul Kumar; Saini, Rajan; Bedi, R. K.

2016-05-06

A kind of hybrid material is prepared by functionalizing multi-wall carbon nanotubes (MWCNTs-COOH) with substituted copper phthalocyanine and the formation of CuPcOC{sub 8}/MWCNTs-COOH hybrid is confirmed by scanning electron microscopy and transmission electron microscopy. The results indicated that on the surface of nanotubes substituted CuPcOC{sub 8} derivatives has been successfully anchored through π-π stacking interaction. The gas sensing application of the fabricated hybrid material is tested upon exposure to different hazardous species, specifically NO{sub 2}, NO, Cl{sub 2} and NH{sub 3} at operating temperature of 150°C. It has been demonstrated that for Cl{sub 2} minimum detection limit of CuPcOC{sub 8}/MWCNTs-COOHmore » hybrid is 100 ppb. The response of hybrid sensor is found to be increased with increase in the concentration of Cl{sub 2}.« less

Sensitized chemiluminescence of 2-phenyl-4,5-di(2-furyl)-1H-imidazole/K₃Fe(CN)₆/propyl gallate system combining with solid-phase extraction for the determination of propyl gallate in edible oil.

PubMed

Kang, Jing; Han, Lu; Chen, Zhonglin; Shen, Jimin; Nan, Jun; Zhang, Yihua

2014-09-15

In this paper, a novel chemiluminescence (CL) method has been developed for the determination of propyl gallate (PG). The proposed method was based on the enhancing effect of PG on the CL signal of 2-phenyl-4,5-di(2-furyl)-1H-imidazole (PDFI) and K3Fe(CN)6 reaction in an alkaline solution. Under the optimum conditions, the enhanced CL intensity was linearly related to the concentration of PG. The linear range of the calibration curve was 0.05-8 μg/mL, and the corresponding detection limit (3σ) was 0.036 μg/mL. The relative standard deviation for determining 1.0 μg/mL PG was 2.8% (n=11). The proposed method has been successfully applied to the determination of PG in edible oil. The edible oil samples were prepared by the solid-phase extraction (SPE) with a C18 column served as the stationary phase. Furthermore, the possible CL mechanism was also discussed briefly based on the photoluminescence (PL) and CL spectra. Copyright © 2014 Elsevier Ltd. All rights reserved.

Determination of 2-methoxyestradiol in serum samples and pharmaceutical preparations by silver nanoparticles-enhanced chemiluminescence.

PubMed

Zhang, Min; Xiao, Xiangqin; Zeng, Wenyuan; Zeng, Xiaoying; Yao, Hanchun

2014-03-01

Silver nanoparticles (AgNPs) exhibited better chemiluminescence (CL) catalysis activity and smaller nanoparticles have stronger catalysis ability in luminol-K3Fe(CN)6 system among the synthesized AgNPs of different size. 10±2 nm nanoparticles was used as catalysts to enhance the reaction sensitivity. It was found that the CL intensity of AgNPs-luminol-K3Fe(CN)6 was strongly inhibited in the presence of 2-methoxyestradiol (2-ME) and the relative CL intensity was in linear correlation with the concentration of 2-ME. Thus, the silver nanoparticles-enhanced CL method for the determination of 2-ME was developed. The proposed method has a detection limit (3 Sb/K) of 5.0×10(-10) mol L(-1) with a relative standard deviation of 0.75% for 5.0×10(-8) mol L(-1) 2-ME. The method was successfully applied for determination of 2-ME in human serum and pharmaceutical preparations. The possible CL reaction mechanism was also discussed briefly. Oxygen radicals played an important role in the catalytic process. Copyright © 2013 Elsevier B.V. All rights reserved.

Determination of dihydralazine based on chemiluminescence resonance energy transfer of hollow carbon nanodots

NASA Astrophysics Data System (ADS)

Han, Suqin; Fan, Zheyan; Chen, Xiaoxia; Wu, Yunfang; Wang, Jianbo

2017-08-01

The famous weak chemiluminescence (CL) system of potassium permanganate and sodium bisulfite (KMnO4-HSO3-) was enhanced by the hollow fluorescent carbon nanodots (HCNs). The investigation of mechanism revealed that the enhanced CL was induced by the excited-state HCNs (HCNs*), which could be produced from the electron-transfer annihilation of positively charged HCNs (HCNsrad +) and negatively charged HCNs (HCNsrad -) as well as by CL resonance energy transfer (CRET) from excited SO2 (SO2*)/1O2 to HCNs. The dihydralazine sulfate (DHZS) had a diminishing effect on the CL of HCNs-KMnO4-HSO3- system due to the competitive consumption of rad O2-. Under the optimal conditions, the reduced CL signal with the concentration of DHZS was linear in the range of 1.0 × 10- 7-7.0 × 10- 5 mol/L with a detection limit of 3.0 × 10- 8 mol/L. The relative standard deviation for seven repeated determination of 5.0 × 10- 6 mol/L DHZS was 2.1%. The established method was applied to the determination of DHZS in pharmaceutical preparations, human urine and plasma samples with good precision and accuracy.

Amperometric Immunosensors for screening of Polycyclic Aromatic Hydrocarbons in water

NASA Astrophysics Data System (ADS)

Ahmad, A.; Paschero, A.; Moore, E.

2011-08-01

An amperometric immunosensor with low limit detection was developed for the screening of polycyclic aromatic hydrocarbons (PAHs) in water. The system was based on detecting the specific substance using an immunological reaction by measuring the chemical responses to specific antibodies. An integrated biochip with a three electrode system was fabricated. Gold was used as the working electrode with platinum was used as the counter electrode. A modified Ag/AgCl reference electrode was employed to enhance the stability of the immunosensors. Indirect competition enzyme-linked immunosorbent assay (ELISA) was carried out within the electrode using alkaline phosphatase (AP) as the labelled-enzyme. The system shows acceptable reproducibility and good stability. The immunosensor exhibited a wide linear response to PAHs. A limit of detection for this sensor was in the range of 1 to 10 ng ml-1 in aqueous sample.

Kinetics and Thermochemistry of ClCO Formation from the Cl + CO Association Reaction

NASA Technical Reports Server (NTRS)

Nicovich, J. M.; Kreutter, K. D.; Wine, P. H.

1997-01-01

Laser flash photolysis of Cl2/CO/M mixtures (M = N2, CO, Ar, CO2) has been employed in conjunction with Cl((sup 2)P(sub J)) detection by time-resolved resonance fluorescence spectroscopy to investigate equilibration kinetics in the reactions Cl((sup 2)P(sub J)) + CO ClCO as a function of temperature (185-260 K) and pressure (14-200 Torr). The association and dissociation reactions are found to be in the low-pressure limit over the range of experimental conditions investigated. In N2 and/or CO buffer gases, the temperature dependences of the ClCO formation and dissociation reaction rate constants are described by the Arrhenius expressions k(sub 1) = (1.05 +/- 0.36) x 10(exp -34) exp[(810 +/- 70)/T] cm(exp 6)/molecules(exp 2).s and k(sub -1) = (4.1 +/- 3.1) x 10(exp -10) exp[(-2960 +/- 60)/T]cu cm/(molecule.s) (errors are 2 sigma). Second- and third-law analyses of the temperature dependence of the equilbrium constant (k/k-1) lead to the following thermodynamic parameters for the association reaction: Delta-H(sub 298) = -7.7 +/- 0.6 kcal/mol, Delta-H(sub 0) = -6.9 +/- 0.7 kcal/mol, Delta-S(sub 298) = -23.8 +/- 2.0 cal/mole.K, Delta-H(sub f,298)(ClCO) = 5.2 +/- 0.6 kcal/mol (errors are 2 sigma). The results repported in this study significantly reduce the uncertainties in all reported kinetic and thermodynamic parameters.

Chemiluminescence microfluidic system of gold nanoparticles enhanced luminol-silver nitrate for the determination of vitamin B12.

PubMed

Kamruzzaman, Mohammad; Alam, Al-Mahmnur; Kim, Kyung Min; Lee, Sang Hak; Kim, Young Ho; Kabir, A N M Hamidul; Kim, Gyu-Man; Dang, Trung Dung

2013-02-01

A rapid and sensitive chemiluminescence (CL) system coupled with a microfluidic chip has been presented to determine vitamin B12 (VB12) based on the reaction of luminol and silver nitrate (AgNO(3)) in the presence of gold nanoparticles (AuNPs). A microfluidic chip was fabricated by a soft-lithographic procedure using polydimethyl siloxane (PDMS) having four inlets and one outlet with a 200 μm wide, 250 μm deep, and 100 mm long microchannel. Ag(+) was used as a chemiluminogenic oxidant in this CL reaction which oxidized luminol to produce strong CL signal in the presence of AuNPs. Luminol reacted with AgNO(3) under the catalysis of AuNPs to produce luminol radicals which reacted with dissolved oxygen and emitted CL light. The proposed CL system was applied to determine the amount of VB12 in VB12 tablets and multivitamin. Under the optimum conditions, the CL intensity of the system was increased with the concentration of VB12 in the range of 0.25-100 ng mL(-1) with the correlation coefficient of 0.9982. The limit of detection was found to be 0.04 ng mL(-1) with the relative standard deviation of 1.56 % for five replicate determinations of 25 ng mL(-1) of VB12. The CL reaction mechanism was demonstrated by UV-visible spectra and CL emission spectra.

Untangling the Causes of Variation in ClNO2 Yield from the WINTER Campaign

NASA Astrophysics Data System (ADS)

Fibiger, D. L.; Lopez-Hilfiker, F.; McDuffie, E. E.; Dubé, W.; Lee, B. H.; Ebben, C. J.; Sparks, T.; Wooldridge, P. J.; Weinheimer, A. J.; Montzka, D.; Schroder, J. C.; Campuzano-Jost, P.; Guo, H.; Sullivan, A.; Dibb, J. E.; Weber, R. J.; Jimenez, J. L.; Cohen, R. C.; Thornton, J. A.; Brown, S. S.

2016-12-01

Nitrogen oxides play a key role in atmospheric chemistry. In the lower troposphere they catalyze ozone (O3) production during the day, while at night they react to form nitric acid and remove O3. While these processes are well studied in summertime, winter measurements are far more limited. While summer has more active photochemistry, in winter there is greater potential for longer-range transport of pollutants as they have longer lifetimes against photochemical or heterogeneous oxidation. As part of the Wintertime INvestigation of Transport, Emission and Reactivity (WINTER) campaign, aircraft-based measurements were made over the northeastern United States of oxidized nitrogen species, their precursors and products. At night, NOX (NO + NO2) reacts with O3 to form N2O5. The N2O5 can then be taken up onto aerosol particles where it forms either two HNO3 or HNO3 and ClNO2. The balance between these pathways is important for atmospheric chemistry the next day, as ClNO2 will photolyze to yield a NO2 molecule and a Cl radical. In contrast, HNO3 does not participate in further radical chemistry. Thus, formation of ClNO2 can lead to longer-range transport of NOX as well as radical production in less polluted areas. Laboratory studies suggest that the yield of ClNO2 is dependent on the relative concentrations of aerosol chloride and liquid water, but it is unknown whether these yields can be accurately predicted based on air mass history or measured ambient aerosol composition. The observed levels of ClNO2 varied significantly throughout the WINTER campaign from below detection limit to over 2 ppbv, while the yield of ClNO2 covered its entire possible range of 0 to 1. In this study we will use the wealth of data and wide range of observed values to constrain which factors are most important in determining ClNO2 yield and to compare these yields to recent parameterizations from laboratory studies.

An ultrasensitive chemiluminescence aptasensor for thrombin detection based on iron porphyrin catalyzing luminescence desorbed from chitosan modified magnetic oxide graphene composite.

PubMed

Sun, Yuanling; Wang, Yanhui; Li, Jianbo; Ding, Chaofan; Lin, Yanna; Sun, Weiyan; Luo, Chuannan

2017-11-01

In this work, an ultrasensitive chemiluminescence (CL) aptasensor was prepared for thrombin detection based on iron porphyrin catalyzing luminol - hydrogen peroxide luminescence under alkaline conditions, and iron porphyrin was desorbed from chitosan modified magnetic oxide graphene composite (CS@Fe 3 O 4 @GO). Firstly, CS@Fe 3 O 4 @GO was prepared. CS@Fe 3 O 4 @GO has advantages of the good biocompatibility and positively charged on its surface of CS, the large specific surface area of GO and the easy separation characteristics of Fe 3 O 4 . GO, Fe 3 O 4 and CS@Fe 3 O 4 @GO were confirmed by transmission electron microscopy (TEM), scanning electron microscope (SEM), fourier transform infrared (FTIR) and X-ray powder diffraction (XRD). Then, thrombin aptamer (T-Apt) and hemin (HM, an iron porphyrin) were sequentially modified on the surface of CS@Fe 3 O 4 @GO to form CS@Fe 3 O 4 @GO@T-Apt@HM. The immobilization properties of CS@Fe 3 O 4 @GO to T-Apt and adsorption properties of CS@Fe 3 O 4 @GO@T-Apt to HM were sequentially researched through the curves of kinetics and the curves of thermodynamics. When thrombin existed in solutions, HM was desorbed from the surface of CS@Fe 3 O 4 @GO@T-Apt@HM owing to the strong specific recognition ability between thrombin and T-Apt, causing the changes of CL signal. Under optimized CL conditions, thrombin could be measured with the linear concentration range of 5.0×10 -15 -2.5×10 -10 mol/L. The detection limit was 1.5×10 -15 mol/L (3δ) while the relative standard deviation (RSD) was 3.2%. Finally, the CS@Fe 3 O 4 @GO@T-Apt@HM-CL aptasensor was used for the determination of thrombin in practical serum samples and recoveries ranged from 95% to 103%. Those satisfactory results revealed potential application of the CS@Fe 3 O 4 @GO@T-Apt@HM-CL aptasensor for thrombin detection in monitoring and diagnosis of human blood diseases. Copyright © 2017 Elsevier B.V. All rights reserved.

Highly selective and sensitive chemiluminescence biosensor for adenosine detection based on carbon quantum dots catalyzing luminescence released from aptamers functionalized graphene@magnetic β-cyclodextrin polymers.

PubMed

Sun, Yuanling; Ding, Chaofan; Lin, Yanna; Sun, Weiyan; Liu, Hao; Zhu, Xiaodong; Dai, Yuxue; Luo, Chuannan

2018-08-15

In this work, a highly selective and sensitive chemiluminescence (CL) biosensor was prepared for adenosine (AD) detection based on carbon quantum dots (CQDs) catalyzing the CL system of luminol-H 2 O 2 under alkaline environment and CQDs was released from the surface of AD aptamers functionalized graphene @ magnetic β-cyclodextrin polymers (GO@Fe 3 O 4 @β-CD@A-Apt). Firstly, GO@Fe 3 O 4 @β-CD and CQDs were prepared and characterized by transmission electron microscopy (TEM), scanning electron microscope (SEM), UV-Vis absorption spectra (UV), fluorescence spectra (FL), fourier transform infrared (FTIR) and X-ray powder diffraction (XRD). For GO@Fe 3 O 4 @β-CD, Fe 3 O 4 was easy to separate, GO had good biocompatibility and large specific surface area, and β-CD further increased the specific surface area of the adenosine polymers (A-Apt) to provided larger binding sites to A-Apt. Then, A-Apt was modified on the surface of GO@Fe 3 O 4 @β-CD while CQDs was modified by ssDNA (a single stranded DNA partially complementary to A-Apt). The immobilization property (GO@Fe 3 O 4 @β-CD to A-Apt) and the adsorption property (GO@Fe 3 O 4 @β-CD@A-Apt to CQDs-ssDNA) were sequentially researched. The base-supported chain-like polymers - GO@Fe 3 O 4 @β-CD@A-Apt/CQDs-ssDNA was successfully obtained. When AD existed, CQDs-ssDNA was released from the surface of GO@Fe 3 O 4 @β-CD@A-Apt and catalyzed CL. After that, under optimized CL conditions, AD could be measured with the linear concentration range of 5.0 × 10 -13 -5.0 × 10 -9 mol/L and the detection limit of 2.1 × 10 -13 mol/L (3δ) while the relative standard deviation (RSD) was 1.4%. Finally, the GO@Fe 3 O 4 @β-CD@A-Apt/CQDs-ssDNA-CL biosensor was used for the determination of AD in urine samples and recoveries ranged from 98.6% to 101.0%. Those satisfactory results illustrated the proposed CL biosensor could achieve highly selective, sensitive and reliable detection of AD and revealed potential application for AD detection in monitoring and diagnosis of human cancers. Copyright © 2018 Elsevier B.V. All rights reserved.

A flow method based on solvent extraction coupled on-line to a reversed micellar mediated chemiluminescence detection for selective determination of gold(III) and gallium(III) in water and industrial samples.

PubMed

Hasanin, Tamer H A; Okamoto, Yasuaki; Fujiwara, Terufumi

2016-02-01

A rapid and sensitive flow method, based on the combination of on-line solvent extraction with reversed micellar mediated chemiluminescence (CL) detection using rhodamine B (RB), was investigated for the selective determination of Au(III) and Ga(III) in aqueous solutions. 2.0 M HCl was the optimum for extracting Au(III) while a 5.0M HCl solution containing 2.5M LiCl was selected as an optimum acidic medium for extraction of Ga(III). The Au(III) and Ga(III) chloro-complex anions were extracted from the above aqueous acidic solutions into toluene as their ion-pair complexes with the protonated RBH(+) ion followed by membrane phase separation in a flow system. In a flow cell of a detector, the extract was mixed with the reversed micellar solution of cetyltrimethylammonium chloride (CTAC) in 1-hexanol-cyclohexane/water (1.0M HCl) containing 0.10 M cerium(IV) and 0.05 M lithium sulfate. Then uptake of the ion-pair by the CTAC reversed micelles and the subsequent CL oxidation of RB with Ce(IV) occurred easily and the CL signals produced were recorded. Using a flow injection system, a detection limit (DL) of 0.4 μM Au(III) and 0.6 μM Ga(III), and linear calibration graphs with dynamic ranges from the respective DLs to 10 μM for Au(III) and Ga(III) were obtained under the optimized experimental conditions. The relative standard deviations (n=6) obtained at 2.0 µM Au(III) and 4.0 µM Ga(III) were 3.0% and 2.4%, respectively. The presented CL methodology has been applied for the determination of Au(III) and Ga(III) in water and industrial samples with satisfactory results. Copyright © 2015 Elsevier B.V. All rights reserved.

A sensitive gold nanoparticles sensing platform based on resonance energy transfer for chemiluminescence light on detection of biomolecules.

PubMed

Qin, Guoxing; Zhao, Shulin; Huang, Yong; Jiang, Jing; Liu, Yi-Ming

2013-08-15

In this article, we report a gold nanoparticles (AuNPs) sensing platform based on chemiluminescence resonance energy transfer (CRET) for light on detection of biomolecules. In designing such a CRET-based biosensing platform, the aptamer was first covalently labeled with a chemiluminescent reagent, N-(4-aminobutyl)-N-ethylisoluminol (ABEI). The ABEI labeled aptamer was then hybridized with AuNPs functionalized ssDNA which was complementary to the aptamer, obtaining the aptasensor. The CRET between ABEI and AuNPs in the aptasensor led to the CL quenching of ABEI. In the presence of a target analyte, it formed a complex with aptamer, and released ABEI-aptamer from AuNPs surface that resulted in CL recovery of ABEI. To test this design, a thrombin (used as a model analyte) aptasensor was prepared and evaluated. The results indicate that the proposed approach is simple and provided a linear range of 50-550 pM for thrombin detection with a detection limit of 15 pM. This new methodology can be easily extended to assay other biomolecules by simply changing the recognition sequence with the substrate aptamer. Copyright © 2013 Elsevier B.V. All rights reserved.

On-line and in-situ detection of polycyclic aromatic hydrocarbons (PAH) on aerosols via thermodesorption and laser-induced fluorescence spectroscopy.

PubMed

Panne, U; Knöller, A; Kotzick, R; Niessner, R

2000-02-01

A fiber optical sensor system for the determination of polycyclic aromatic hydrocarbons (PAH) on aerosols by laser-induced, time-resolved fluorescence is combined with a thermodesorption device. The sensor system is based on an aerosol flow cell, which is fibre-optically coupled to a pulsed nitrogen laser for excitation and the detection system. Time-resolved fluorescence emission spectra are detected by a monochromator equipped with a photomultiplier and a fast digital storage oscilloscope. The analytical figures of merit of the thermodenuder are reported for benzo[a]pyrene, benzo[b]fluoranthene, and benzo[ghi]-perylene on ultrafine soot and NaCl aerosols. By thermodesorption of the PAH, problems due to quenching of the PAH fluorescence by the bulk aerosol material or excimer formation on the aerosol surface were avoided. For the PAH under study, the sensitivity was improved considerably and detection limits between 110 and 850 ng m(-3) were attained, while a response time of 2-3 min was achieved with the thermodenuder. A calibration for PAH on ultrafine soot and NaCl aerosols was established independent of the aerosol substrate.

Subpicomolar sensing of hydrogen peroxide with ovalbumin-embedded chitosan/polystyrene sulfonate multilayer membrane.

PubMed

Divyalakshmi, T V; Sreedhanya, S; Akhil, G; Aravindakumar, C T; Aravind, Usha K

2013-09-01

The use of ovalbumin (OVA)-immobilized layer-by-layer-assembled chitosan/polystyrene sulfonate membranes for the detection of hydrogen peroxide (H2O2) at subpicomolar levels is reported. The detection of mercuric chloride (HgCl2) and potassium iodide (KI) was also investigated. While the detection limits of HgCl2 and KI remained in the micromolar concentration range, H2O2 could be sensed to a remarkably lower range (subpicomolar). Analysis of fluorescence quenching data of OVA by H2O2 using Stern-Volmer plots revealed a static quenching mechanism with high Stern-Volmer quenching constant (9.10×10(12) L mol(-1)) and k (5.82×10(21) L mol(-1) s(-1)). The possibility of the conformational transition of OVA in the immobilized state is discussed using steady-state and time-resolved spectroscopic techniques. The resulting increased accessibility of tryptophan residues together with the reversibility of the bilayer for the sensing of H2O2 is also illustrated. Copyright © 2013 Elsevier Inc. All rights reserved.

A flow injection chemiluminescence method for determination of nalidixic acid based on KMnO4-morin sensitized with CdS quantum dots

NASA Astrophysics Data System (ADS)

Khataee, Alireza; Lotfi, Roya; Hasanzadeh, Aliyeh; Iranifam, Mortaza; Joo, Sang Woo

2016-02-01

A simple and sensitive flow injection chemiluminescence (CL) method was developed for determination of nalidixic acid by application of CdS quantum dots (QDs) in KMnO4-morin CL system in acidic medium. Optical and structural features of L-cysteine capped CdS quantum dots which were synthesized via hydrothermal approach were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL), and ultraviolet-visible (UV-Vis) spectroscopy. Moreover, the potential mechanism of the proposed CL method was described using the results of the kinetic curves of CL systems, the spectra of CL, PL and UV-Vis analyses. The CL intensity of the KMnO4-morin-CdS QDs system was considerably increased in the presence of nalidixic acid. Under the optimum condition, the enhanced CL intensity was linearly proportional to the concentration of nalidixic acid in the range of 0.0013 to 21.0 mg L- 1, with a detection limit of (3σ) 0.003 mg L- 1. Also, the proposed CL method was utilized for determination of nalidixic acid in environmental water samples, and commercial pharmaceutical formulation to approve its applicability. Furthermore, corona discharge ionization ion mobility spectrometry (CD-IMS) method was utilized for determination of nalidixic acid and the results of real sample analysis by two proposed methods were compared. Comparison the analytical features of these methods represented that the proposed CL method is preferable to CD-IMS method for determination of nalidixic acid due to its high sensitivity and precision.

A flow injection chemiluminescence method for determination of nalidixic acid based on KMnO₄-morin sensitized with CdS quantum dots.

PubMed

Khataee, Alireza; Lotfi, Roya; Hasanzadeh, Aliyeh; Iranifam, Mortaza; Joo, Sang Woo

2016-02-05

A simple and sensitive flow injection chemiluminescence (CL) method was developed for determination of nalidixic acid by application of CdS quantum dots (QDs) in KMnO4-morin CL system in acidic medium. Optical and structural features of L-cysteine capped CdS quantum dots which were synthesized via hydrothermal approach were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL), and ultraviolet-visible (UV-Vis) spectroscopy. Moreover, the potential mechanism of the proposed CL method was described using the results of the kinetic curves of CL systems, the spectra of CL, PL and UV-Vis analyses. The CL intensity of the KMnO4-morin-CdS QDs system was considerably increased in the presence of nalidixic acid. Under the optimum condition, the enhanced CL intensity was linearly proportional to the concentration of nalidixic acid in the range of 0.0013 to 21.0 mg L(-1), with a detection limit of (3σ) 0.003 mg L(-1). Also, the proposed CL method was utilized for determination of nalidixic acid in environmental water samples, and commercial pharmaceutical formulation to approve its applicability. Furthermore, corona discharge ionization ion mobility spectrometry (CD-IMS) method was utilized for determination of nalidixic acid and the results of real sample analysis by two proposed methods were compared. Comparison the analytical features of these methods represented that the proposed CL method is preferable to CD-IMS method for determination of nalidixic acid due to its high sensitivity and precision. Copyright © 2015 Elsevier B.V. All rights reserved.

Analysis of nanoliter samples of electrolytes using a flow-through microfluorometer.

PubMed

Zhelyaskov, V R; Liu, S; Broderick, M P

2000-04-01

Several techniques have been developed to study the transport properties of nanoliter samples of renal tubule segments, such as continuous flow colorimetry and continuous fluorometry. We have extended the capability of the NANOFLO, a flow-through microfluorometer, designed for measurement of carbon dioxide, urea, ammonia, glucose, lactate, etc., to analyze sodium, calcium and chloride ions, using three commercially available fluorescent indicators for intracellular and extracellular measurements. The selection of fluorescent indicator for each electrolyte was dependent on the optimal match of the dissociation constant and the analyte concentration range of interest. Using Fluo-3 dye we achieved a detection limit for Ca2+ of 0.1 pmol and selectivity over Mg2+ of between 7:1 to 10:1. Using sodium green dye we achieved detection limit for Na+ of 12 pmol and a selectivity over K+ of 40:1. The detection limit for Cl- using lucigenin dye was 10 pmol. This technique can be readily adapted for the measurement of other physiologically important ultralow volume.

Electrochemical sample matrix elimination for trace-level potentiometric detection with polymeric membrane ion-selective electrodes.

PubMed

Chumbimuni-Torres, Karin Y; Calvo-Marzal, Percy; Wang, Joseph; Bakker, Eric

2008-08-01

Potentiometric sensors are today sufficiently well understood and optimized to reach ultratrace level (subnanomolar) detection limits for numerous ions. In many cases of practical relevance, however, a high electrolyte background hampers the attainable detection limits. A particularly difficult sample matrix for potentiometric detection is seawater, where the high saline concentration forms a major interfering background and reduces the activity of most trace metals by complexation. This paper describes for the first time a hyphenated system for the online electrochemically modulated preconcentration and matrix elimination of trace metals, combined with a downstream potentiometric detection with solid contact polymeric membrane ion-selective microelectrodes. Following the preconcentration at the bismuth-coated electrode, the deposited metals are oxidized and released to a medium favorable to potentiometric detection, in this case calcium nitrate. Matrix interferences arising from the saline sample medium are thus circumvented. This concept is successfully evaluated with cadmium as a model trace element and offers potentiometric detection down to low parts per billion levels in samples containing 0.5 M NaCl background electrolyte.

Electrochemical Sample Matrix Elimination for Trace Level Potentiometric Detection with Polymeric Membrane Ion-Selective Electrodes

PubMed Central

Chumbimuni-Torres, Karin Y.; Calvo-Marzal, Percy; Wang, Joseph; Bakker, Eric

2008-01-01

Potentiometric sensors are today sufficiently well understood and optimized to reach ultra-trace level (sub-nanomolar) detection limits for numerous ions. In many cases of practical relevance, however, a high electrolyte background hampers the attainable detection limits. A particularly difficult sample matrix for potentiometric detection is seawater, where the high saline concentration forms a major interfering background and reduces the activity of most trace metals by complexation. This paper describes for the first time a hyphenated system for the online electrochemically modulated preconcentration and matrix elimination (EMPM) of trace metals, combined with a downstream potentiometric detection with solid contact polymeric membrane ion-selective microelectrodes. Following the preconcentration at the bismuth coated electrodes, the deposited metals are oxidized and released to a medium favorable to potentiometric detection, in this case calcium nitrate. Matrix interferences arising from the saline sample medium are thus circumvented. This concept is successfully evaluated with cadmium as a model trace element and offers potentiometric detection down to low parts per billion levels in samples containing 0.5 M NaCl background electrolyte. PMID:18570385

Natural chlorate in the environment: Application of a new IC-ESI/MS/MS method with a Cl18O3- internal standard

USGS Publications Warehouse

Rao, Balaji; Hatzinger, Paul B.; Böhlke, John Karl; Sturchio, Neil C.; Andraski, Brian J.; Eckardt, Frank D.; Jackson, W. Andrew

2010-01-01

A new ion chromatography electrospray tandem mass spectrometry (IC-ESI/MS/MS) method has been developed for quantification and confirmation of chlorate (ClO3−) in environmental samples. The method involves the electro-chemical generation of isotopically labeled chlorate internal standard (Cl18O3−) using 18O water (H218O). The standard was added to all samples prior to analysis thereby minimizing the matrix effects that are associated with common ions without the need for expensive sample pretreatments. The method detection limit (MDL) for ClO3− was 2 ng L−1 for a 1 mL volume sample injection. The proposed method was successfully applied to analyze ClO3− in difficult environmental samples including soil and plant leachates. The IC-ESI/MS/MS method described here was also compared to established EPA method 317.0 for ClO3− analysis. Samples collected from a variety of environments previously shown to contain natural perchlorate (ClO4−) occurrence were analyzed using the proposed method and ClO3− was found to co-occur with ClO4− at concentrations ranging from <2 ng L−1 in precipitation from Texas and Puerto Rico to >500 mg kg−1 in caliche salt deposits from the Atacama Desert in Chile. Relatively low concentrations of ClO3− in some natural groundwater samples (<0.1 μg L−1) analyzed in this work may indicate lower stability when compared to ClO4− in the subsurface. The high concentrations of ClO3− in caliches and soils (3−6 orders of magnitude greater) as compared to precipitation samples indicate that ClO3−, like ClO4−, may be atmospherically produced and deposited, then concentrated in dry soils, and is possibly a minor component in the biogeochemical cycle of chlorine.

Natural chlorate in the environment: application of a new IC-ESI/MS/MS method with a Cl¹⁸O₃-internal standard.

PubMed

Balaji Rao, Balaji Rao; Hatzinger, Paul B; Böhlke, John Karl; Sturchio, Neil C; Andraski, Brian J; Eckardt, Frank D; Jackson, W Andrew

2010-11-15

A new ion chromatography electrospray tandem mass spectrometry (IC-ESI/MS/MS) method has been developed for quantification and confirmation of chlorate (ClO₃⁻) in environmental samples. The method involves the electrochemical generation of isotopically labeled chlorate internal standard (Cl¹⁸O₃⁻) using ¹⁸O water (H₂¹⁸O) he standard was added to all samples prior to analysis thereby minimizing the matrix effects that are associated with common ions without the need for expensive sample pretreatments. The method detection limit (MDL) for ClO₃⁻ was 2 ng L⁻¹ for a 1 mL volume sample injection. The proposed method was successfully applied to analyze ClO₃⁻ in difficult environmental samples including soil and plant leachates. The IC-ESI/MS/MS method described here was also compared to established EPA method 317.0 for ClO₃⁻ analysis. Samples collected from a variety of environments previously shown to contain natural perchlorate (ClO₄⁻) occurrence were analyzed using the proposed method and ClO₃⁻ was found to co-occur with ClO₄⁻ at concentrations ranging from < 2 ng L⁻¹ in precipitation from Texas and Puerto Rico to >500 mg kg⁻¹ in caliche salt deposits from the Atacama Desert in Chile. Relatively low concentrations of ClO₃⁻ in some natural groundwater samples (0.1 µg L⁻¹) analyzed in this work may indicate lower stability when compared to ClO₄⁻ in the subsurface. The high concentrations ClO₃⁻ in caliches and soils (3-6 orders of magnitude greater) as compared to precipitation samples indicate that ClO₃⁻, like ClO₄⁻, may be atmospherically produced and deposited, then concentrated in dry soils, and is possibly a minor component in the biogeochemical cycle of chlorine.

Study on the reaction mechanism and the static injection chemiluminescence method for detection of acetaminophen.

PubMed

Wu, Yongjun; Zhang, Huili; Yu, Songcheng; Yu, Fei; Li, Yanqiang; Zhang, Hongquan; Qu, Lingbo; Harrington, Peter de B

2013-01-01

Acetaminophen, also called paracetamol, is found in Tylenol, Excedrin and other products as over-the-counter medicines. In this study, acetaminophen as a luminol signal enhancer was used in the chemiluminescence (CL) substrate solution of horseradish peroxidase (HRP) for the first time. The use of acetaminophen in the luminol-HRP-H2O2 system affected not only the intensity of the obtained signal, but also its kinetics. It was shown that acetaminophen was to be a potent enhancer of the luminol-HRP-H2O2 system. A putative enhancement mechanism for the luminol-H2O2-HRP-acetaminophen system is presented. The resonance of the nucleophilic amide group and the benzene ring of acetaminophen structure have a great effect on O-H bond dissociation energy of the phenol group and therefore on phenoxyl radical stabilization. These radicals act as mediators between HRP and luminol in an electron transfer reaction that generates luminol radicals and subsequently light emission, in which the intensity of CL is enhanced in the presence of acetaminophen. In addition, a simple method was developed to detect acetaminophen by static injection CL based on the enhanced CL system of luminol-H2O2-HRP by acetaminophen. Experimental conditions, such as pH and concentrations of substrates, have been examined and optimized. The proposed method exhibited good performance, the linear range was from 0.30 to 7.5 mM, the relative standard deviation was 1.86% (n = 10), limit of detection was 0.16 mM and recovery was 99 ± 4%. Copyright © 2013 John Wiley & Sons, Ltd.

Orderly arranged fluorescence dyes as a highly efficient chemiluminescence resonance energy transfer probe for peroxynitrite.

PubMed

Wang, Zhihua; Teng, Xu; Lu, Chao

2015-03-17

Chemiluminescence (CL) probes for reactive oxygen species (ROS) are commonly based on a redox reaction between a CL reagent and ROS, leading to poor selectivity toward a specific ROS. The energy-matching rules in the chemiluminescence resonance energy transfer (CRET) process between a specific ROS donor and a suitable fluorescence dye acceptor is a promising method for the selective detection of ROS. Nevertheless, higher concentrations of fluorescence dyes can lead to the intractable aggregation-caused quenching effect, decreasing the CRET efficiency. In this report, we fabricated an orderly arranged structure of calcein-sodium dodecyl sulfate (SDS) molecules to improve the CRET efficiency between ONOOH* donor and calcein acceptor. Such orderly arranged calcein-SDS composites can distinguish peroxynitrite (ONOO(-)) from a variety of other ROS owing to the energy matching in the CRET process between ONOOH* donor and calcein acceptor. Under the optimal experimental conditions, ONOO(-) could be assayed in the range of 1.0-20.0 μM, and the detection limit for ONOO(-) [signal-to-noise ratio (S/N) = 3] was 0.3 μM. The proposed strategy has been successfully applied in both detecting ONOO(-) in cancer mouse plasma samples and monitoring the generation of ONOO(-) from 3-morpholinosydnonimine (SIN-1). Recoveries from cancer mouse plasma samples were in the range of 96-105%. The success of this work provides a unique opportunity to develop a CL tool to monitor ONOO(-) with high selectivity in a specific manner. Improvement of selectivity and sensitivity of CL probes holds great promise as a strategy for developing a wide range of probes for various ROS by tuning the types of fluorescence dyes.

A chemiluminescence biosensor based on the adsorption recognition function between Fe3O4@SiO2@GO polymers and DNA for ultrasensitive detection of DNA.

PubMed

Sun, Yuanling; Li, Jianbo; Wang, Yanhui; Ding, Chaofan; Lin, Yanna; Sun, Weiyan; Luo, Chuannan

2017-05-05

In this work, a chemiluminescence (CL) biosensor was prepared for ultrasensitive determination of deoxyribonucleic acid (DNA) based on the adsorption recognition function between core-shell Fe 3 O 4 @SiO 2 - graphene oxide (Fe 3 O 4 @SiO 2 @GO) polymers and DNA. The Fe 3 O 4 @SiO 2 @GO polymers were composed by GO and magnetite nanoparticles. And the core-shell polymers were confirmed by Scanning Electron Microscope (SEM), X-Ray Powder Diffraction (XRD) and Fourier Transform Infrared (FTIR). Then Fe 3 O 4 @SiO 2 @GO was modified by DNA. Based on the principle of complementary base, Fe 3 O 4 @SiO 2 @GO-DNA was introduced to the CL system and the selectivity, sensitivity of DNA detection was significantly improved. The adsorption properties of Fe 3 O 4 @SiO 2 @GO to DNA were researched through the adsorption equilibrium, adsorption kinetic and thermodynamics. Under optimized CL conditions, DNA could be assayed with the linear concentration range of 5.0×10 -12 -2.5×10 -11 mol/L. The detection limit was 1.7×10 -12 mol/L (3δ) and the relative standard deviation (RSD) was 3.1%. The biosensor was finally used for the determination of DNA in laboratory samples and recoveries ranged from 99% to 103%. The satisfactory results revealed the potential application of Fe 3 O 4 @SiO 2 @GO-DNA-CL biosensor in the diagnosis and the treatment of human genetic diseases. Copyright © 2017 Elsevier B.V. All rights reserved.

Multifunctional reduced graphene oxide trigged chemiluminescence resonance energy transfer: Novel signal amplification strategy for photoelectrochemical immunoassay of squamous cell carcinoma antigen.

PubMed

Zhang, Yan; Sun, Guoqiang; Yang, Hongmei; Yu, Jinghua; Yan, Mei; Song, Xianrang

2016-05-15

Herein, a photoelectrochemical (PEC) immunoassay is constructed for squamous cell carcinoma antigen (SCCA) detection using zinc oxide nanoflower-bismuth sulfide (Bi2S3) composites as photoactive materials and reduced graphene oxide (rGO) as signal labels. Horseradish peroxidase is used to block sites against nonspecific binding, and then participated in luminol-based chemiluminescence (CL) system. The induced CL emission is acted as an inner light source to excite photoactive materials, simplifying the instrument. A novel signal amplification strategy is stem from rGO because of the rGO acts as an energy acceptor, while luminol serves as a donor to rGO, triggering the CL resonance energy transfer phenomenon between luminol and rGO. Thus, the efficient CL emission to photoactive materials decreases. Furthermore, the signal amplification caused by rGO labeled signal antibodies is related to photogenerated electron-hole pairs: perfect matching of energy levels between rGO and Bi2S3 makes rGO a sink to capture photogenerated electrons from Bi2S3; the increased steric hindrance hinders the electron donor to the surface of Bi2S3 for reaction with the photogenerated holes. On the basis of the novel signal amplification strategy, the proposed immunosensor exhibits excellent analytical performance for PEC detection of SCCA, ranging from 0.8 pg mL(-1) to 80 ng mL(-1) with a low detection limit of 0.21 pg mL(-1). Meanwhile, the designed signal amplification strategy provides a general format for future development of PEC assays. Copyright © 2015 Elsevier B.V. All rights reserved.

Density-based parallel skin lesion border detection with webCL

PubMed Central

2015-01-01

Background Dermoscopy is a highly effective and noninvasive imaging technique used in diagnosis of melanoma and other pigmented skin lesions. Many aspects of the lesion under consideration are defined in relation to the lesion border. This makes border detection one of the most important steps in dermoscopic image analysis. In current practice, dermatologists often delineate borders through a hand drawn representation based upon visual inspection. Due to the subjective nature of this technique, intra- and inter-observer variations are common. Because of this, the automated assessment of lesion borders in dermoscopic images has become an important area of study. Methods Fast density based skin lesion border detection method has been implemented in parallel with a new parallel technology called WebCL. WebCL utilizes client side computing capabilities to use available hardware resources such as multi cores and GPUs. Developed WebCL-parallel density based skin lesion border detection method runs efficiently from internet browsers. Results Previous research indicates that one of the highest accuracy rates can be achieved using density based clustering techniques for skin lesion border detection. While these algorithms do have unfavorable time complexities, this effect could be mitigated when implemented in parallel. In this study, density based clustering technique for skin lesion border detection is parallelized and redesigned to run very efficiently on the heterogeneous platforms (e.g. tablets, SmartPhones, multi-core CPUs, GPUs, and fully-integrated Accelerated Processing Units) by transforming the technique into a series of independent concurrent operations. Heterogeneous computing is adopted to support accessibility, portability and multi-device use in the clinical settings. For this, we used WebCL, an emerging technology that enables a HTML5 Web browser to execute code in parallel for heterogeneous platforms. We depicted WebCL and our parallel algorithm design. In addition, we tested parallel code on 100 dermoscopy images and showed the execution speedups with respect to the serial version. Results indicate that parallel (WebCL) version and serial version of density based lesion border detection methods generate the same accuracy rates for 100 dermoscopy images, in which mean of border error is 6.94%, mean of recall is 76.66%, and mean of precision is 99.29% respectively. Moreover, WebCL version's speedup factor for 100 dermoscopy images' lesion border detection averages around ~491.2. Conclusions When large amount of high resolution dermoscopy images considered in a usual clinical setting along with the critical importance of early detection and diagnosis of melanoma before metastasis, the importance of fast processing dermoscopy images become obvious. In this paper, we introduce WebCL and the use of it for biomedical image processing applications. WebCL is a javascript binding of OpenCL, which takes advantage of GPU computing from a web browser. Therefore, WebCL parallel version of density based skin lesion border detection introduced in this study can supplement expert dermatologist, and aid them in early diagnosis of skin lesions. While WebCL is currently an emerging technology, a full adoption of WebCL into the HTML5 standard would allow for this implementation to run on a very large set of hardware and software systems. WebCL takes full advantage of parallel computational resources including multi-cores and GPUs on a local machine, and allows for compiled code to run directly from the Web Browser. PMID:26423836

Density-based parallel skin lesion border detection with webCL.

PubMed

Lemon, James; Kockara, Sinan; Halic, Tansel; Mete, Mutlu

2015-01-01

Dermoscopy is a highly effective and noninvasive imaging technique used in diagnosis of melanoma and other pigmented skin lesions. Many aspects of the lesion under consideration are defined in relation to the lesion border. This makes border detection one of the most important steps in dermoscopic image analysis. In current practice, dermatologists often delineate borders through a hand drawn representation based upon visual inspection. Due to the subjective nature of this technique, intra- and inter-observer variations are common. Because of this, the automated assessment of lesion borders in dermoscopic images has become an important area of study. Fast density based skin lesion border detection method has been implemented in parallel with a new parallel technology called WebCL. WebCL utilizes client side computing capabilities to use available hardware resources such as multi cores and GPUs. Developed WebCL-parallel density based skin lesion border detection method runs efficiently from internet browsers. Previous research indicates that one of the highest accuracy rates can be achieved using density based clustering techniques for skin lesion border detection. While these algorithms do have unfavorable time complexities, this effect could be mitigated when implemented in parallel. In this study, density based clustering technique for skin lesion border detection is parallelized and redesigned to run very efficiently on the heterogeneous platforms (e.g. tablets, SmartPhones, multi-core CPUs, GPUs, and fully-integrated Accelerated Processing Units) by transforming the technique into a series of independent concurrent operations. Heterogeneous computing is adopted to support accessibility, portability and multi-device use in the clinical settings. For this, we used WebCL, an emerging technology that enables a HTML5 Web browser to execute code in parallel for heterogeneous platforms. We depicted WebCL and our parallel algorithm design. In addition, we tested parallel code on 100 dermoscopy images and showed the execution speedups with respect to the serial version. Results indicate that parallel (WebCL) version and serial version of density based lesion border detection methods generate the same accuracy rates for 100 dermoscopy images, in which mean of border error is 6.94%, mean of recall is 76.66%, and mean of precision is 99.29% respectively. Moreover, WebCL version's speedup factor for 100 dermoscopy images' lesion border detection averages around ~491.2. When large amount of high resolution dermoscopy images considered in a usual clinical setting along with the critical importance of early detection and diagnosis of melanoma before metastasis, the importance of fast processing dermoscopy images become obvious. In this paper, we introduce WebCL and the use of it for biomedical image processing applications. WebCL is a javascript binding of OpenCL, which takes advantage of GPU computing from a web browser. Therefore, WebCL parallel version of density based skin lesion border detection introduced in this study can supplement expert dermatologist, and aid them in early diagnosis of skin lesions. While WebCL is currently an emerging technology, a full adoption of WebCL into the HTML5 standard would allow for this implementation to run on a very large set of hardware and software systems. WebCL takes full advantage of parallel computational resources including multi-cores and GPUs on a local machine, and allows for compiled code to run directly from the Web Browser.

A fast stir bar sorptive extraction method for the analysis of geosmin and 2-methylisoborneol in source and drinking water.

PubMed

Bauld, T; Teasdale, P; Stratton, H; Uwins, H

2007-01-01

The presence of unpleasant taste and odour in drinking water is an ongoing aesthetic concern for water providers worldwide. The need for a sensitive and robust method capable of analysis in both natural and treated waters is essential for early detection of taste and odour events. The purpose of this study was to develop and optimise a fast stir bar sorptive extraction (SBSE) method for the analysis of geosmin and 2-methylisoborneol (MIB) in both natural water and drinking water. Limits of detection with the optimised fast method (45 min extraction time at 60 degrees C using 24 microL stir bars) were 1.1 ng/L for geosmin and 4.2 ng/L for MIB. Relative standard deviations at the detection limits were under 17% for both compounds. Use of multiple stir bars can be used to decrease the detection limits further. The use of 25% NaCl and 5% methanol sample modifiers decreased the experimental recoveries. Likewise, addition of 1 mg/L and 1.5 mg/L NaOCI decreased the recoveries and this effect was not reversed by addition of 10% thiosulphate. The optimised method was used to measure geosmin concentrations in treated and untreated drinking water. MIB concentrations were below the detection limits in these waters.

Flow injection chemiluminescence determination of lercanidipine based on N-chlorosuccinimide-eosin Y post-chemiluminescence reaction.

PubMed

Wang, Guowei; Zhao, Fang; Gao, Ying

2014-12-01

A novel post-chemiluminescence (PCL) reaction was discovered when lercanidipine was injected into the CL reaction mixture of N-chlorosuccinimide with alkaline eosin Y in the presence of cetyltrimethylammonium bromide (CTAB), where eosin Y was used as the CL reagent and CTAB as the surfactant. Based on this observation, a simple and highly sensitive PCL method combined with a flow injection (FI) technique was developed for the assay of lercanidipine. Under optimum conditions, the CL signal was linearly related to the concentration of lercanidipine in the range 7.0 × 10(-10) to 3.0 × 10(-6)  g/mL with a detection limit of 2.3 × 10(-10) g/mL (3σ). The relative standard deviation (RSD) was 2.1% for 1.0 × 10(-8) g/mL lercanidipine (n = 13). The proposed method had been applied to the estimation of lercanidipine in tablets and human serum samples with satisfactory results. The possible CL mechanism is also discussed briefly. Copyright © 2014 John Wiley & Sons, Ltd.

Deletion of RhoA in Progesterone Receptor-Expressing Cells Leads to Luteal Insufficiency and Infertility in Female Mice.

PubMed

El Zowalaty, Ahmed E; Li, Rong; Zheng, Yi; Lydon, John P; DeMayo, Francesco J; Ye, Xiaoqin

2017-07-01

Ras homolog gene family, member A (RhoA) is widely expressed throughout the female reproductive system. To assess its role in progesterone receptor-expressing cells, we generated RhoA conditional knockout mice RhoAd/d (RhoAf/f-Pgr-Cre+/-). RhoAd/d female mice had comparable mating activity, serum luteinizing hormone, prolactin, and estradiol levels and ovulation with control but were infertile with progesterone insufficiency, indicating impaired steroidogenesis in RhoAd/d corpus luteum (CL). RhoA was highly expressed in wild-type luteal cells and conditionally deleted in RhoAd/d CL. Gestation day 3.5 (D3.5) RhoAd/d ovaries had reduced numbers of CL, less defined corpus luteal cord formation, and disorganized CL collagen IV staining. RhoAd/d CL had lipid droplet and free cholesterol accumulation, indicating the availability of cholesterol for steroidogenesis, but disorganized β-actin and vimentin staining, indicating disrupted cytoskeleton integrity. Cytoskeleton is important for cytoplasmic cholesterol movement to mitochondria and for regulating mitochondria. Dramatically reduced expression of mitochondrial markers heat shock protein 60 (HSP60), voltage-dependent anion channel, and StAR was detected in RhoAd/d CL. StAR carries out the rate-limiting step of steroidogenesis. StAR messenger RNA expression was reduced in RU486-treated D3.5 wild-type CL and tended to be induced in progesterone-treated D3.5 RhoAd/d CL, with parallel changes of HSP60 expression. These data demonstrated the in vivo function of RhoA in CL luteal cell cytoskeleton integrity, cholesterol transport, StAR expression, and progesterone synthesis, and a positive feedback on StAR expression in CL by progesterone signaling. These findings provide insights into mechanisms of progesterone insufficiency.

Novel and versatile solid-state chemiluminescence sensor based on TiO2-Ru(bpy)32+ nanoparticles for pharmaceutical drugs detection

NASA Astrophysics Data System (ADS)

Al-Hetlani, Entesar; Amin, Mohamed O.; Madkour, Metwally

2018-02-01

This work describes a novel and versatile solid-state chemiluminescence sensor for analyte detection using TiO2-Ru(bpy)32+-Ce(IV). Herein, we report the synthesis, characterization, optimization and application of a new type of hybrid nanoparticles (NPs). Mesoporous TiO2-Ru(bpy)32+ NPs were prepared using a modified sol-gel method by incorporating Ru(bpy)32+ into the initial reaction mixture at various concentrations. The resultant bright orange precipitate was characterized via transmission electron microscopy, N2 sorpometry, inductively coupled plasma-optical emission spectrometer (ICP-OES), Raman and UV-Vis spectroscopy techniques. The concentration of Ru(bpy)32+ complex in the NPs was quantified using ICP-OES, and its chemiluminescence (CL) response was measured and compared with the same concentration in the liquid phase using oxalate as model analyte. The results showed that this type of hybrid material exhibited a higher CL signal compared with the liquid phase due to the enlarged surface area of the hybrid NPs ( 149.6 m2/g). The amount of TiO2-Ru(bpy)32+ NPs and the effect of the analyte flow rate were also investigated to optimize the CL signal. The optimized system was further used to detect oxalate and two pharmaceutical drugs, namely, imipramine and promazine. The linear range for both drugs was 1-100 pm with limits of detection (LOD) of 0.1 and 0.5 pm, respectively. This approach is considered to be simple, low cost and facile and can be applied to a wide range of analytes.

Method for Detection and Enumeration of Cryptosporidium parvum Oocysts in Feces, Manures, and Soils

PubMed Central

Kuczynska, Ewa; Shelton, Daniel R.

1999-01-01

Eight concentration and purification methods were evaluated to determine percentages of recovery of Cryptosporidium parvum oocysts from calf feces. The NaCl flotation method generally resulted in the highest percentages of recovery. Based on the percentages of recovery, the amounts of fecal debris in the final oocyst preparations, the relatively short processing time (<3 h), and the low expense, the NaCl flotation method was chosen for further evaluation. Extraction efficiency was evaluated by using oocyst concentrations of 25, 50, 102, 103, 104, and 105 oocysts g of bovine feces−1. The percentages of recovery ranged from 10.8% (25 oocysts g−1) to 17.0% (104 oocysts g−1) (r2 = 0.996). A conservative estimate of the detection limit for bovine feces is ca. 30 oocysts g of feces−1. Percentages of recovery were determined for six different types of animal feces (cow, horse, pig, sheep, deer, and chicken feces) at a single oocyst concentration (104 oocysts g−1). The percentages of recovery were highest for bovine feces (17.0%) and lowest for chicken feces (3.2%). Percentages of recovery were determined for bovine manure after 3 to 7 days of storage. The percentages of recovery ranged from 1.9 to 3.5% depending on the oocyst concentration, the time of storage, and the dispersing solution. The percentages of oocyst recovery from soils were evaluated by using different flotation solutions (NaCl, cold sucrose, ZnSO4), different dispersing solutions (Triton X-100, Tween 80, Tris plus Tween 80), different dispersion techniques (magnetic stirring, sonication, blending), and different dispersion times (5, 15, and 30 min). Twenty-five-gram soil samples were used to reduce the spatial variability. The highest percentages of recovery were obtained when we used 50 mM Tris–0.5% Tween 80 as the dispersing solution, dispersion for 15 min by stirring, and saturated NaCl as the flotation solution. The percentages of oocyst recovery from freshly spiked sandy loam, silty clay loam, and clay loam soils were ca. 12 to 18, 8, and 6%, respectively. The theoretical detection limits were ca. 1 to 2 oocysts g of soil−1 depending on the soil type. The percentages of recovery without dispersant (distilled H2O or phosphate-buffered saline) were less than 0.1%, which indicated that oocysts adhere to soil particles. The percentages of recovery decreased with storage time, although the addition of dispersant (Tris-Tween 80) before storage appeared to partially prevent adhesion. These data indicate that the NaCl flotation method is suitable for routine detection and enumeration of oocysts from feces, manures, soils, or soil-manure mixtures. PMID:10388670

Maximum time-dependent space-charge limited diode currents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Griswold, M. E.; Fisch, N. J.

Recent papers claim that a one dimensional (1D) diode with a time-varying voltage drop can transmit current densities that exceed the Child-Langmuir (CL) limit on average, apparently contradicting a previous conjecture that there is a hard limit on the average current density across any 1D diode, as t → ∞, that is equal to the CL limit. However, these claims rest on a different definition of the CL limit, namely, a comparison between the time-averaged diode current and the adiabatic average of the expression for the stationary CL limit. If the current were considered as a function of the maximummore » applied voltage, rather than the average applied voltage, then the original conjecture would not have been refuted.« less

Genetic segregation in a high-yielding streptomycin-producing strain of Streptomyces griseus.

PubMed

Roth, M; Schwalenberg, B; Reiche, R; Noack, D; Geuther, R; Eritt, I

1982-01-01

The streptomycin-producing Streptomyces griseus HP spontaneously segregated non-reverting derivatives with altered phenotypes. Clones characterized by increased spore formation and decreased streptomycin production were found. Two other types of derivatives were defective in aerial mycelium and streptomycin formation as well, but differed in the capacity to synthesize a yellow pigment. These derivatives were examined with respect to further properties. The stability of S. griseus HP was investigated in relation to conditions of continuous culture. Both at 26 and 30 degrees C, under glycerol and NH4Cl limitation a rapid segregation and enrichment of streptomycin-non-producing derivatives occurred. At 34 degrees C and glycerol limitation segregation began only after about 35 generations of continuous culture. In NH4Cl-limited chemostats the original strain was stable during 80 generations. In the course of the continuous culture experiments it was shown that the onset of genetic segregation within mycelia can be detected before it becomes obvious in colonies grown from the mycelia. This was achieved by fractionation of the mycelia by protoplast formation and subsequent plating on regeneration medium allowing colony growth and differentiation.

Synthesis of Nitrogen-Doped Graphene Quantum Dots at Low Temperature for Electrochemical Sensing Trinitrotoluene.

PubMed

Cai, Zhewei; Li, Fumin; Wu, Ping; Ji, Lijuan; Zhang, Hui; Cai, Chenxin; Gervasio, Dominic F

2015-12-01

Nitrogen-doped graphene quantum dots (N-GQDs) are synthesized at low temperature as a new catalyst allowing electrochemical detection of 2,4,6-trinitrotoluene (TNT). N-GQDs are made by an oxidative ultrasonication of graphene oxide (GO) forming nanometer-sized species, which are then chemically reduced and nitrogen doped by reacting with hydrazine. The as-synthesized N-GQDs have an average diameter of ∼2.5 nm with an N/C atomic ratio of up to ∼6.4%. To detect TNT, TNT is first accumulated on N-GQDs modified glassy carbon (N-GQDs/GC) electrode by holding the electrode at a 0 V versus Ag/AgCl for 150 s in an aqueous TNT solution. Next, the N-GQDs/GC electrode with accumulated TNT is transferred to a fresh PBS solution (0.1 M, pH 7.0, without TNT), where the TNT reduction current at -0.36 V versus Ag/AgCl in a linear scan voltammogram (LSV) shows a linear response to TNT concentration in the aqueous solution from 1 to 400 ppb, with a correlation coefficient of 0.999, a detection limit of 0.2 ppb at a signal/noise (S/N) of 3, and a detection sensitivity of 363 ± 7 mA mM(-1) cm(-2). The detection limit of 0.2 ppb of TNT for this new method is much lower than 2 ppb set by the U.S. Environmental Protection Agency for drinking water. Therefore, N-GQDs allow an electrochemical method for assaying TNT in drinking water to determine if levels of TNT are safe or not.

Corrosion fatigue of Inconel 718 and Incoloy 903

NASA Technical Reports Server (NTRS)

Franklin, D. B.; Nelson, E. E.

1981-01-01

Corrosion fatigue tests were conducted on Inconel 718 and Incoloy 903 in distilled water, 500 ppm NaCl, and 3.5% NaCl. Results were compared to the endurance limit in air. For Inconel 718, the corrosion fatigue strength (CFS) IN 3.5% NaCl WAS 328 MPa or 75 percent of the endurance limit. For Incoloy 903, the CFS ranged from 234 MPa in distilled water (68 percent of the endurance limit) to 103 MPa in 3.5% NaCl (30 percent of the endurance limit). Results indicate that, for components which have limited fatigue life, an evaluation of the combined effects of fatigue and the corrosive atmosphere must be considered in projecting useful lifetimes.

Magnetic bead-sensing-platform-based chemiluminescence resonance energy transfer and its immunoassay application.

PubMed

Qin, Guoxin; Zhao, Shulin; Huang, Yong; Jiang, Jing; Ye, Fanggui

2012-03-20

A competitive immunoassay based on chemiluminescence resonance energy transfer (CRET) on the magnetic beads (MBs) is developed for the detection of human immunoglobulin G (IgG). In this protocol, carboxyl-modified MBs were conjugated with horseradish peroxidase (HRP)-labeled goat antihuman IgG (HRP-anti-IgG) and incubated with a limited amount of fluorescein isothiocyanate (FITC)-labeled human IgG to immobilize the antibody-antigen immune complex on the surface of the MBs, which was further incubated with the target analyte (human IgG) for competitive immunoreaction and separated magnetically to remove the supernatant. The chemiluminescence (CL) buffer (containing luminol and H(2)O(2)) was then added, and the CRET from donor luminol to acceptor FITC in the immunocomplex on the surface of MBs occured immediately. The present protocol was evaluated for the competitive immunoassay of human IgG, and a linear relationship between CL intensity ratio (R = I(425)/I(525)) and human IgG concentration in the range of 0.2-4.0 nM was obtained with a correlation coefficient of 0.9965. The regression equation was expressed as R = 1.9871C + 2.4616, and a detection limit of 2.9 × 10(-11) M was obtained. The present method was successfully applied for the detection of IgG in human serum. The results indicate that the present protocol is quite promising for the application of CRET in immunoassays. It could also be developed for detection of other antigen-antibody immune complexes by using the corresponding antigens and respective antibodies.

Mass Spectrometry Identification of N-Chlorinated Dipeptides in Drinking Water.

PubMed

Huang, Guang; Jiang, Ping; Li, Xing-Fang

2017-04-04

We report the identification of N-chlorinated dipeptides as chlorination products in drinking water using complementary high-resolution quadrupole time-of-flight (QTOF) and quadrupole ion-trap mass spectrometry techniques. First, three model dipeptides, tyrosylglycine (Tyr-Gly), tyrosylalanine (Tyr-Ala), and phenylalanylglycine (Phe-Gly), reacted with sodium hypochlorite, and these reaction solutions were analyzed by QTOF. N-Cl-Tyr-Gly, N,N-di-Cl-Tyr-Gly, N-Cl-Phe-Gly, N,N-di-Cl-Phe-Gly, N-Cl-Tyr-Ala, and N,N-di-Cl-Tyr-Ala were identified as the major products based on accurate masses, 35 Cl/ 37 Cl isotopic patterns, and MS/MS spectra. These identified N-chlorinated dipeptides were synthesized and found to be stable in water over 10 days except N,N-di-Cl-Phe-Gly. To enable sensitive detection of N-chlorinated dipeptides in authentic water, we developed a high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method with multiple reaction monitoring (MRM) mode. N-Cl-Tyr-Gly, N,N-di-Cl-Tyr-Gly, N-Cl-Phe-Gly, N-Cl-Tyr-Ala, and N,N-di-Cl-Tyr-Ala along with their corresponding dipeptides were detected in authentic tap water samples. The dipeptides were clearly detected in the raw water, but the N-chlorinated dipeptides were at background levels. These results suggest that the N-chlorinated dipeptides are produced by chlorination. This study has identified N-chlorinated dipeptides as new disinfection byproducts in drinking water. The strategy developed in this study can be used to identify chlorination products of other peptides in drinking water.

Determination of folates by HPLC-chemiluminescence using a ruthenium(II)-cerium(IV) system, and its application to pharmaceutical preparations and supplements.

PubMed

Ikeda, Rie; Ichiyama, Kosuke; Tabuchi, Naoto; Wada, Mitsuhiro; Kuroda, Naotaka; Nakashima, Kenichiro

2014-11-01

A chemiluminescence (CL) reaction of folic acid (FA) with ruthenium (II) and cerium (IV) was applied to quantify FA-related compounds such as FA, dihydrofolic acid, tetrahydrofolic acid, 5-methyltetrahydrofolic acid, 5-formyltetrahydrofolic acid and methotrexate (MTX). Among the FAs, 5-methyltetrahydrofolic acid provided the highest CL intensity. HPLC-CL detection of FA was applied to quantify FA in pharmaceutical preparations and supplements. Analytical samples were separated on a semi-micro ODS column with a mixture of 20 mM phosphate buffer (pH 5.7) and acetonitrile (94 : 6, v/v %). The separated samples were mixed with a post-column CL reagent consisting of 1.5 mM Ru(bipy)3 (2+) and 1.0 mM Ce(SO4)2 , then the generated CL was monitored. The calibration range for FA was 10-100 μM and the limit of detection was 1.34 μM (signal-to-noise ratio of 3). Repeatabilities were 4.2, 4.6 and 5.0 RSD% (10, 25, 50 μM), and the recoveries for FA supplement, vitamin B complex supplement and FA-containing medication (tablet) were 102.4 ± 10.5, 103.3 ± 13.3 and 100.3 ± 8.5%, respectively. The described method is robust against changes in the chromatographic parameters of ± 3.3 or ± 1.5%. The measured FA content corresponded well to the labeled content of FA-containing products (100.6-104.9%), demonstrating the precision and accuracy of this method for the evaluation of FA pharmaceutical preparations. Copyright © 2014 John Wiley & Sons, Ltd.

Directional Limits on Persistent Gravitational Waves Using LIGO S5 Science Data

NASA Technical Reports Server (NTRS)

Abadie, J.; Abbott, B. P.; Abbott, R.; Abernathy, M.; Accadia, T.; Acernese, F.; Adams, C.; Adhikari, R.; Ajith, P.; Allen, B.;

Determination of tannic acid in industrial wastewater based on chemiluminescence system of KIO₄-H₂O₂-Tween40.

PubMed

Xie, Cheng-gen; Li, Huai-fen

2010-01-01

The oxidation reaction of H₂O₂ with KIO₄ can produce chemiluminescence (CL) in the presence of the surfactant Tween40 and the CL intensity of the CL system KIO₄-H₂O₂-Tween40 can be strikingly enhanced after injection of tannic acid. On this basis, a flow injection method with CL detection was established for the determination of tannic acid. The method is simple, rapid and effective to determine tannic acid in the range of 7.0 × 10(-9) to 1.0 × 10(-5) mol/L with a determination limit of 2.3 × 10(-9) mol/L. The relative standard deviation is 2.6% for the determination of 5.0 × 10(-6 )mol/L tannic acid (n = 11). The method has been applied to determine the content of tannic acid in industrial wastewater with satisfactory results. It is believed that the CL reaction formed singlet oxygen (1)O(2)* and the emission was from an excited oxygen molecular pair O₂(¹Δ(g))O₂(¹∑⁻(g)) in the KIO₄-H₂O₂-Tween40 reaction. Tween40 played an important role in enhancing stabilization of the excited oxygen molecular pair O₂(¹Δ(g))O₂(¹∑⁻(g)) and in increasing CL intensity. Copyright © 2010 John Wiley & Sons, Ltd.

Very high energy observations of the BL Lac objects 3C 66A and OJ 287

NASA Astrophysics Data System (ADS)

Lindner, T.; Hanna, D. S.; Kildea, J.; Ball, J.; Bramel, D. A.; Carson, J.; Covault, C. E.; Driscoll, D.; Fortin, P.; Gingrich, D. M.; Jarvis, A.; Mueller, C.; Mukherjee, R.; Ong, R. A.; Ragan, K.; Scalzo, R. A.; Williams, D. A.; Zweerink, J.

2007-11-01

Using the Solar Tower Atmospheric Cherenkov Effect Experiment (STACEE), we have observed the BL Lac objects 3C 66A and OJ 287. These are members of the class of low-frequency-peaked BL Lac objects (LBLs) and are two of the three LBLs predicted by Costamante and Ghisellini [L. Costamante, G. Ghisellini, Astron. Astrophys. 384 (2002) 56] to be potential sources of very high energy (>100 GeV) gamma-ray emission. The third candidate, BL Lacertae, has recently been detected by the MAGIC collaboration [J. Albert et al., arXiv:astro-ph/0703084v1 (2007)]. Our observations have not produced detections; we calculate a 99% CL upper limit of flux from 3C 66A of 0.15 Crab flux units and from OJ 287 our limit is 0.52 Crab. These limits assume a Crab-like energy spectrum with an effective energy threshold of 185 GeV.

Study on the luminescence behavior of sulfobutylether-β-cyclodextrin with risperidone and its analytical application.

PubMed

Wu, Min; Chen, Donghua; Song, Zhenghua

2012-10-01

The interaction of sulfobutylether-β-cyclodextrin (SBE-β-CD) with risperidone (RISP) was first described with luminol-SBE-β-CD chemiluminescence (CL) system by flow injection analysis (FIA). In luminol-SBE-β-CD CL system, the 1:1 SBE-β-CD···luminol(*) complexation could enhance CL intensity of luminol and produce the effect of complexation enhancement of CL (CEC). It was found that RISP could quench the CL intensity of SBE-β-CD···luminol(*) and caused the effect of complexation enhancement of quenching (CEQ), the formation constant K(R-CD) 3.4×10(4) L mol(-1) and the stoichiometric ratio 1:1 of RISP···SBE-β-CD complex were obtained by the proposed CL model. Association degree α 0.036 of RISP···SBE-β-CD complex was also given by CL method. Based on the linear relationship to the decrement of luminol-SBE-β-CD-RISP CL intensity and the logarithm of RISP concentration, RISP also can be quantified in the linear range of 3.0-500.0 nmol L(-1) with a detection limit of 1.0 nmol L(-1) (3σ). The proposed method was successfully applied to monitoring excreted RISP in human urine. It was found that RISP reached its maximum after oral administration for 1.5 h with the total excretion of 14.26% within 8.5 h; the elimination rate constant k and half-life time t(1/2) were 0.474 and 1.5 h, respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

Nitryl chloride (ClNO2): UV/vis absorption spectrum between 210 and 296 K and O(3P) quantum yield at 193 and 248 nm.

PubMed

Ghosh, Buddhadeb; Papanastasiou, Dimitrios K; Talukdar, Ranajit K; Roberts, James M; Burkholder, James B

2012-06-21

Recent studies have shown that the UV/vis photolysis of nitryl chloride (ClNO2) can be a major source of reactive chlorine in the troposphere. The present work reports measurements of the ClNO2 absorption spectrum and its temperature dependence between 210 and 296 K over the wavelength range 200–475 nm using diode array spectroscopy. The room temperature spectrum obtained in this work was found to be in good agreement with the results from Ganske et al. (J. Geophys. Res. 1992, 97, 7651) over the wavelength range common to both studies (200–370 nm) but differs systematically from the currently recommended spectrum for use in atmospheric models. The present results lead to a decrease in the calculated atmospheric ClNO2 photolysis rate by 30%. Including the temperature dependence of the ClNO2 spectrum decreases the calculated atmospheric photolysis rate at lower temperatures (higher altitudes) even further. A parametrization of the wavelength and temperature dependence of the ClNO2 spectrum is presented. O(3P) quantum yields, Φ(ClNO2)(O), in the photolysis of ClNO2 at 193 and 248 nm were measured at 296 K using pulsed laser photolysis combined with atomic resonance fluorescence detection of O(3P) atoms. Φ(ClNO2)(O)(λ) was found to be 0.67 ± 0.12 and 0.15 ± 0.03 (2σ error limits, including estimated systematic errors) at 193 and 248 nm, respectively, indicating that multiple dissociation channels are active in the photolysis of ClNO2 at these wavelengths. The Φ(ClNO2)(O)(λ) values obtained in this work are discussed in light of previous ClNO2 photodissociation studies and the differences are discussed.

SERS spectral study of HAuCl4-cysteine nanocatalytic reaction and its application for detection of heparin sodium with label-free VB4r molecular probe

NASA Astrophysics Data System (ADS)

Wang, Xiaoliang; Jiang, Caina; Qin, Yanna; Peng, Yutao; Wen, Guiqing; Liang, Aihui; Jiang, Zhiliang

2017-04-01

In the presence of nanocatalyst, L-cysteine reduce HAuCl4 rapidly to form gold nanoparticles (AuNP), and a quick nanocatalytic preparation procedure was established for Au/AuNP sol with highly active surface enhanced Raman scattering (SERS) effect and good stability. The nanoreaction was also studied by absorption, resonance Rayleigh scattering (RRS), transmission electron microscopy (TEM) and energy spectra. In the selected conditions, the analyte heparin sodium (HS) could react with victoria blue 4 R (VB4r) to form associated complexes which have very weak SERS effect to make the SERS signals decrease. The SERS signals at 1617 cm-1 reduced linearly with HS concentration increasing. Upon addition of FeCl3, it hydrolyzed to form stable Fe(OH)3 sol platform that carried SERS active Au/AuNPs to enhance the sensitivity. Accordingly, we established a SERS quantitative analysis method in the sol substrate of Fe(OH)3-Au/AuNPs, with a linear range of 0.5-75 ng/mL HS and a detection limit of 0.2 ng/mL. HS in real samples was determined, with a relative standard deviation of 2.65-7.63% and a recovery of 99.3-101%.

Carbon Nanotube Thread Electrochemical Cell: Detection of Heavy Metals.

PubMed

Zhao, Daoli; Siebold, David; Alvarez, Noe T; Shanov, Vesselin N; Heineman, William R

2017-09-19

In this work, all three electrodes in an electrochemical cell were fabricated based on carbon nanotube (CNT) thread. CNT thread partially insulated with a thin polystyrene coating to define the microelectrode area was used as the working electrode; bare CNT thread was used as the auxiliary electrode; and a micro quasi-reference electrode was fabricated by electroplating CNT thread with Ag and then anodizing it in chloride solution to form a layer of AgCl. The Ag|AgCl coated CNT thread electrode provided a stable potential comparable to the conventional liquid-junction type Ag|AgCl reference electrode. The CNT thread auxiliary electrode provided a stable current, which is comparable to a Pt wire auxiliary electrode. This all-CNT thread three electrode cell has been evaluated as a microsensor for the simultaneous determination of trace levels of heavy metal ions by anodic stripping voltammetry (ASV). Hg 2+ , Cu 2+ , and Pb 2+ were used as a representative system for this study. The calculated detection limits (based on the 3σ method) with a 120 s deposition time are 1.05, 0.53, and 0.57 nM for Hg 2+ , Cu 2+ , and Pb 2+ , respectively. These electrodes significantly reduce the dimensions of the conventional three electrode electrochemical cell to the microscale.

Determination of sulpiride in pharmaceutical preparations and biological fluids using a Cr (III) enhanced chemiluminescence method.

PubMed

Khan, Muhammad Naeem; Jan, Muhammad Rasul; Shah, Jasmin; Lee, Sang Hak; Kim, Young Ho

2013-01-01

A highly sensitive and simple method for identifying sulpiride in pharmaceutical formulations and biological fluids is presented. The method is based on increased chemiluminescence (CL) intensity of a luminol-H2O2 system in response to the addition of Cr (III) under alkaline conditions. The CL intensity of the luminol-H2O2-Cr (III) system was greatly enhanced by the addition of sulpiride and the CL intensity was proportional to the concentration of sulpiride in a sample solution. Various parameters affecting the CL intensity were systematically investigated and optimized for determination of the sulpiride in a sample. Under the optimum conditions, the CL intensity was proportional to the concentration of sulpiride in the range of 0.068-4.0 µg/mL, with a good correlation coefficient of 0.997. The limit of detection (LOD) and limit of quantification (LOQ) were found to be 8.50 × 10(-6) µg/mL and 2.83 × 10(-5) µg/mL, respectively. The method presented here produced good reproducibility with a relative standard deviation (RSD) of 2.70% (n = 7). The effects of common excipients and metal ions were studied for their interference effect. The method was validated statistically through recovery studies and successfully applied for the determination of sulpiride in pure form, pharmaceutical preparations and spiked human plasma samples. The percentage recoveries were found to range from 99.10 to 100.05% for pure form, 98.12 to 100.18% for pharmaceutical preparations and 97.9 to 101.4% for spiked human plasma. Copyright © 2012 John Wiley & Sons, Ltd.

A validated silver-nanoparticle-enhanced chemiluminescence method for the determination of citalopram in pharmaceutical preparations and human plasma.

PubMed

Khan, Muhammad Naeem; Jan, Muhammad Rasul; Shah, Jasmin; Lee, Sang Hak

2014-05-01

A simple and sensitive chemiluminescence (CL) method was developed for the determination of citalopram in pharmaceutical preparations and human plasma. The method is based on the enhancement of the weak CL signal of the luminol-H2 O2 system. It was found that the CL signal arising from the reaction between alkaline luminol and H2 O2 was greatly increased by the addition of silver nanoparticles in the presence of citalopram. Prepared silver nanoparticles (AgNPs) were characterized by UV-visible spectroscopy and transmission electron microscopy (TEM). Various experimental parameters affecting CL intensity were studied and optimized for the determination of citalopram. Under optimized experimental conditions, CL intensity was found to be proportional to the concentration of citalopram in the range 40-2500 ng/mL, with a correlation coefficient of 0.9997. The limit of detection (LOD) and limit of quantification (LOQ) of the devised method were 3.78 and 12.62 ng/mL, respectively. Furthermore, the developed method was found to have excellent reproducibility with a relative standard deviation (RSD) of 3.65% (n = 7). Potential interference by common excipients was also studied. The method was validated statistically using recovery studies and was successfully applied to the determination of citalopram in the pure form, in pharmaceutical preparations and in spiked human plasma samples. Percentage recoveries were found to range from 97.71 to 101.99% for the pure form, from 97.84 to 102.78% for pharmaceutical preparations and from 95.65 to 100.35% for spiked human plasma. Copyright © 2013 John Wiley & Sons, Ltd.

Diffusion of Antimicrobials Across Silicone Hydrogel Contact Lenses.

PubMed

Zambelli, Alison M; Brothers, Kimberly M; Hunt, Kristin M; Romanowski, Eric G; Nau, Amy C; Dhaliwal, Deepinder K; Shanks, Robert M Q

2015-09-01

To measure the diffusion of topical preparations of moxifloxacin, amphotericin B (AmB), and polyhexamethylene biguanide (PHMB) through silicone hydrogel (SH) contact lenses (CLs) in vitro. Using an in vitro model, the diffusion of three antimicrobials through SH CLs was measured. Diffused compounds were measured using a spectrophotometer at set time points over a period of 4 hr. The amount of each diffused antimicrobial was determined by comparing the experimental value with a standard curve. A biological assay was performed to validate the CL diffusion assay by testing antimicrobial activity of diffused material against lawns of susceptible bacteria (Staphylococcus epidermidis) and yeast (Saccharomyces cerevisiae). Experiments were repeated at least two times with a total of at least four independent replicates. Our data show detectable moxifloxacin and PHMB diffusion through SH CLs at 30 min, whereas AmB diffusion remained below the limit of detection within the 4-hr experimental period. In the biological assay, diffused moxifloxacin demonstrated microbial killing starting at 20 min on bacterial lawns, whereas PHMB and AmB failed to demonstrate killing on microbial lawns over the course of the 60-min experiment. In vitro diffusion assays demonstrate limited penetration of certain anti-infective agents through SH CLs. Further studies regarding the clinical benefit of using these agents along with bandage CL for corneal pathologic condition are warranted.

SEVEN-YEAR WILKINSON MICROWAVE ANISOTROPY PROBE (WMAP ) OBSERVATIONS: COSMOLOGICAL INTERPRETATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Komatsu, E.; Smith, K. M.; Spergel, D. N.

2011-02-01

The combination of seven-year data from WMAP and improved astrophysical data rigorously tests the standard cosmological model and places new constraints on its basic parameters and extensions. By combining the WMAP data with the latest distance measurements from the baryon acoustic oscillations (BAO) in the distribution of galaxies and the Hubble constant (H{sub 0}) measurement, we determine the parameters of the simplest six-parameter {Lambda}CDM model. The power-law index of the primordial power spectrum is n{sub s} = 0.968 {+-} 0.012 (68% CL) for this data combination, a measurement that excludes the Harrison-Zel'dovich-Peebles spectrum by 99.5% CL. The other parameters, includingmore » those beyond the minimal set, are also consistent with, and improved from, the five-year results. We find no convincing deviations from the minimal model. The seven-year temperature power spectrum gives a better determination of the third acoustic peak, which results in a better determination of the redshift of the matter-radiation equality epoch. Notable examples of improved parameters are the total mass of neutrinos, {Sigma}M{sub {nu}} < 0.58 eV(95%CL), and the effective number of neutrino species, N{sub eff} = 4.34{sup +0.86}{sub -0.88} (68% CL), which benefit from better determinations of the third peak and H{sub 0}. The limit on a constant dark energy equation of state parameter from WMAP+BAO+H{sub 0}, without high-redshift Type Ia supernovae, is w = -1.10 {+-} 0.14 (68% CL). We detect the effect of primordial helium on the temperature power spectrum and provide a new test of big bang nucleosynthesis by measuring Y{sub p} = 0.326 {+-} 0.075 (68% CL). We detect, and show on the map for the first time, the tangential and radial polarization patterns around hot and cold spots of temperature fluctuations, an important test of physical processes at z = 1090 and the dominance of adiabatic scalar fluctuations. The seven-year polarization data have significantly improved: we now detect the temperature-E-mode polarization cross power spectrum at 21{sigma}, compared with 13{sigma} from the five-year data. With the seven-year temperature-B-mode cross power spectrum, the limit on a rotation of the polarization plane due to potential parity-violating effects has improved by 38% to {Delta}{alpha} = -1.{sup o}1 {+-} 1.{sup o}4(statistical) {+-} 1.{sup o}5(systematic) (68% CL). We report significant detections of the Sunyaev-Zel'dovich (SZ) effect at the locations of known clusters of galaxies. The measured SZ signal agrees well with the expected signal from the X-ray data on a cluster-by-cluster basis. However, it is a factor of 0.5-0.7 times the predictions from 'universal profile' of Arnaud et al., analytical models, and hydrodynamical simulations. We find, for the first time in the SZ effect, a significant difference between the cooling-flow and non-cooling-flow clusters (or relaxed and non-relaxed clusters), which can explain some of the discrepancy. This lower amplitude is consistent with the lower-than-theoretically expected SZ power spectrum recently measured by the South Pole Telescope Collaboration.« less

Enhanced chemiluminescence of carminic acid-permanganate by CdS quantum dots and its application for sensitive quenchometric flow injection assays of cloxacillin.

PubMed

Khataee, Alireza; Hasanzadeh, Aliyeh; Lotfi, Roya; Joo, Sang Woo

2016-05-15

A novel chemiluminescence (CL) system is introduced based on the oxidation of carminic acid by KMnO4 in acidic conditions. CdS quantum dots (QDs) were synthesized using a facile hydrothermal method which efficiently enhanced the intensity of the CL system. A possible mechanism for the proposed system is presented using the kinetic curves, CL spectra, photoluminescence (PL), and ultraviolet-visible (UV-Vis) analysis. The emission intensity of the KMnO4-carminic acid-CdS QDs system was quenched in the presence of a trace level of cloxacillin. Based on this quenching effect, a novel and sensitive flow injection CL method was developed for determining cloxacillin concentrations. At optimal experimental conditions, the decreased CL intensity had a good linear relation with the cloxacillin concentration in the range of 0.008 to 22.0 mg L(-1). The detection limit (3σ) was 5.8 µg L(-1). The precision of the method was calculated by analyzing samples containing 4.0 mg L(-1) of cloxacillin (n=11), and the relative standard deviations (RSD%) were 2.08%. The feasibility of the method is also demonstrated for determining cloxacillin concentrations in environmental water samples and a pharmaceutical formulation. Copyright © 2016 Elsevier B.V. All rights reserved.

Flow injection chemiluminescence determination of loxoprofen and naproxen with the acidic permanganate-sulfite system.

PubMed

Wang, Li-Juan; Tang, Yu-Hai; Liu, Yang-Hao

2011-02-01

A novel flow injection chemiluminescence (CL) method for the determination of loxoprofen and naproxen was proposed based on the CL system of KMnO 4 , and Na 2 SO 3 in acid media. The CL intensity of KMnO 4 -Na 2 SO 3 was greatly enhaneed in the presence of loxoprofen and naproxen. The mechanism of the CL reaction was studied by the kinetic proecss and UV-vis absorption and the conditions were optimized. Under optimized conditions, the CL intensity was linear with loxoprofen and naproxen concentration in the range of 7.0 × 10 -8 - 1.0 × 10 -5 g/mL and 2.0 × 10 -7 - 4.0 × 10 -6 g/mL with the detection limit of 2.0 × 10 -8 g/mL and 3.0 × 10 -8 g/mL (S/N = 3), respectively. Thc relative standard deviations were 2.39% and 1.37% for 5.0 × 10 -7 g/mL naproxen and 5.0 × 10 -7 g/mL loxoprofen ( n = 10), respectively. The proposed method was satisfactorily applied to thc determination of loxoprofen and naproxen in pharmaceutical preparations.

Sanitizing radish seeds by simultaneous treatments with gaseous chlorine dioxide, high relative humidity, and mild heat.

PubMed

Bang, Jihyun; Choi, Moonhak; Son, Hyeri; Beuchat, Larry R; Kim, Yoonsook; Kim, Hoikyung; Ryu, Jee-Hoon

2016-11-21

Sanitizing radish seeds intended for edible sprout production was achieved by applying simultaneous treatments with gaseous chlorine dioxide (ClO 2 ), high relative humidity (RH, 100%), and mild heat (55°C). Gaseous ClO 2 was produced from aqueous ClO 2 (0.66ml) by mixing sulfuric acid (5% w/v) with sodium chlorite (10 mg/mL) in a sealed container (1.8L). Greater amounts of gaseous ClO 2 were measured at 23% RH (144ppm after 6h) than at 100% RH (66ppm after 6h); however, the lethal activity of gaseous ClO 2 against naturally occurring mesophilic aerobic bacteria (MAB) on radish seeds was significantly enhanced at 100% RH. For example, when exposed to gaseous ClO 2 at 23% RH, the number of MAB on radish seeds decreased from 3.7logCFU/g to 2.6logCFU/g after 6h. However, when exposed to gaseous ClO 2 at 100% RH for 6h, the MAB population decreased to 0.7logCFU/g after 6h. Gaseous ClO 2 was produced in higher amounts at 55°C than at 25°C, but decreased more rapidly over time at 55°C than at 25°C. The lethal activity of gaseous ClO 2 against MAB on radish seeds was greater at 55°C than at 25°C. When radish seeds were treated with gaseous ClO 2 (peak concentration: 195ppm) at 100% RH and 55°C, MAB were reduced to populations below the detectable level (<-0.7logCFU/g) within 2h without decreasing the seed germination rate (97.7%). The lethality of combined treatments against artificially inoculated Escherichia coli O157:H7 was also evaluated. When exposed to gaseous ClO 2 at 100% RH and 55°C for 6h, the initial number of E. coli O157:H7 (3.5logCFU/g) on radish seeds decreased to below the detection limit (0.7logCFU/g) by direct plating but it was not eliminated from seeds. The germination rate of radish seeds was not significantly (P>0.05) decreased after treatment for 6h. The information reported here will be useful when developing decontamination strategies for producing microbiologically safe radish seed sprouts. Copyright © 2016. Published by Elsevier B.V.

Evaluation of current operating standards for chlorine dioxide in disinfection of dump tank and flume for fresh tomatoes.

PubMed

Tomás-Callejas, Alejandro; López-Velasco, Gabriela; Valadez, Angela M; Sbodio, Adrian; Artés-Hernández, Francisco; Danyluk, Michelle D; Suslow, Trevor V

2012-02-01

Standard postharvest unit operations that rely on copious water contact, such as fruit unloading and washing, approach the criteria for a true critical control point in fresh tomato production. Performance data for approved sanitizers that reflect commercial systems are needed to set standards for audit compliance. This study was conducted to evaluate the efficacy of chlorine dioxide (ClO(2)) for water disinfection as an objective assessment of recent industry-adopted standards for dump tank and flume management in fresh tomato packing operations. On-site assessments were conducted during eight temporally distinct shifts in two Florida packinghouses and one California packinghouse. Microbiological analyses of incoming and washed fruit and dump and flume system water were evaluated. Water temperature, pH, turbidity, conductivity, and oxidation-reduction potential (ORP) were monitored. Reduction in populations of mesophilic and coliform bacteria on fruit was not significant, and populations were significantly higher (P < 0.05) after washing. Escherichia coli was near the limit of detection in dump tanks but consistently below the detection limit in flumes. Turbidity and conductivity increased with loads of incoming tomatoes. Water temperature varied during daily operations, but pH and ORP mostly remained constant. The industry standard positive temperature differential of 5.5°C between water and fruit pulp was not maintained in tanks during the full daily operation. ORP values were significantly higher in the flume than in the dump tank. A positive correlation was found between ORP and temperature, and negative correlations were found between ORP and turbidity, total mesophilic bacteria, and coliforms. This study provides in-plant data indicating that ClO(2) can be an effective sanitizer in flume and spray-wash systems, but current operational limitations restrict its performance in dump tanks. Under current conditions, ClO(2) alone is unlikely to allow the fresh tomato industry to meet its microbiological quality goals under typical commercial conditions.

76 FR 477 - Airworthiness Directives; Bombardier, Inc. Model CL-600-2A12 (CL-601) and CL-600-2B16 (CL-601-3A...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-01-05

... to these aircraft if Bombardier Service Bulletin (SB) 601-0590 [Scheduled Maintenance Instructions... information: Challenger 601 Time Limits/Maintenance Checks, PSP 601-5, Revision 38, dated June 19, 2009. Challenger 601 Time Limits/Maintenance Checks, PSP 601A-5, Revision 34, dated June 19, 2009. Challenger 604...

Molecular emission in laser-induced breakdown spectroscopy: An investigation of its suitability for chlorine quantification on Mars

NASA Astrophysics Data System (ADS)

Vogt, D. S.; Rammelkamp, K.; Schröder, S.; Hübers, H. W.

2018-03-01

The intensity of the molecular CaCl emission in LIBS spectra is examined in order to evaluate its suitability for the detection of chlorine in a Martian environment. Various mixtures resembling Martian targets with varying Cl content are investigated under simulated Martian conditions. The reactions leading to the formation of CaCl are modeled based on reaction kinetics and are used to fit the measured CaCl band intensities. MgCl bands are also investigated as potential alternatives to CaCl, but no MgCl bands can be identified in samples containing both Mg and Cl. The study confirms that CaCl is well suited for the indirect detection of chlorine, but finds a strong dependence on the concentrations of Ca and Cl in the sample. Spectra from samples with a high chlorine concentration can have low-intensity CaCl emission due to a deficiency of Ca. A qualitative estimate of the sample composition is possible based on the ratio of the band intensity of CaCl to the intensity of Ca emission lines. Time-resolved measurements show that the CaCl concentration in the plasma is highest after about 1 μs.

Improved sensitivity via layered-double-hydroxide-uniformity-dependent chemiluminescence.

PubMed

Li, Zenghe; Wang, Dan; Yuan, Zhiqin; Lu, Chao

2016-12-01

In the last two decades nanoparticles have been widely applied to enhance chemiluminescence (CL). The morphology of nanoparticles has an important influence on nanoparticle-amplified CL. However, studies of nanoparticle-amplified CL focus mainly on the size and shape effects, and no attempt has been made to explore the influence of uniformity in nanoparticle-amplified CL processes. In this study we have investigated nanoparticle uniformity in the luminol-H 2 O 2 CL system using layered double hydroxides (LDHs) as a model material. The results demonstrated that the uniformity of LDHs played a key role in CL amplification. A possible mechanism is that LDHs with high uniformity possess abundant catalytic active sites, which results in high CL intensity. Meanwhile, the sensitivity for H 2 O 2 detection was increased by one order of magnitude (1.0 nM). Moreover, the uniform-LDH-amplified luminol CL could be applied to selective detection of glucose in human plasma samples. Furthermore, such a uniformity-dependent CL enhancement effect could adapted to other redox CL systems-for example, the peroxynitrous acid (ONOOH) CL system.

Anti-α-Gal antibodies detected by novel neoglycoproteins as a diagnostic tool for Old World cutaneous leishmaniasis caused by Leishmania major.

PubMed

Subramaniam, Krishanthi S; Austin, Victoria; Schocker, Nathaniel S; Montoya, Alba L; Anderson, Matthew S; Ashmus, Roger A; Mesri, Mina; Al-Salem, Waleed; Almeida, Igor C; Michael, Katja; Acosta-Serrano, Alvaro

2018-06-14

Outbreaks of Old World cutaneous leishmaniasis (CL) have significantly increased due to the conflicts in the Middle East, with most of the cases occurring in resource-limited areas such as refugee settlements. The standard methods of diagnosis include microscopy and parasite culture, which have several limitations. To address the growing need for a CL diagnostic that can be field applicable, we have identified five candidate neoglycoproteins (NGPs): Galα (NGP3B), Galα(1,3)Galα (NGP17B), Galα(1,3)Galβ (NGP9B), Galα(1,6)[Galα(1,2)]Galβ (NGP11B), and Galα(1,3)Galβ(1,4)Glcβ (NGP1B) that are differentially recognized in sera from individuals with Leishmania major infection as compared with sera from heterologous controls. These candidates contain terminal, non-reducing α-galactopyranosyl (α-Gal) residues, which are known potent immunogens to humans. Logistic regression models found that NGP3B retained the best diagnostic potential (area under the curve from receiver-operating characteristic curve = 0.8). Our data add to the growing body of work demonstrating the exploitability of the human anti-α-Gal response in CL diagnosis.

Enhancing the chemiluminescence intensity of a KMnO4 formaldehyde system for estimating the total phenolic content in honey samples using a novel nanodroplet mixing approach in a microfluidics platform.

PubMed

Al Lawati, Haider A J; Al Mughairy, Baqia; Al Lawati, Iman; Suliman, FakhrEldin O

2018-04-30

A novel mixing approach was utilized with a highly sensitive chemiluminescence (CL) method to determine the total phenolic content (TPC) in honey samples using an acidic potassium permanganate-formaldehyde system. The mixing approach was based on exploiting the mixing efficiency of nanodroplets generated in a microfluidic platform. Careful optimization of the instrument setup and various experimental conditions were employed to obtain excellent sensitivity. The mixing efficiency of the droplets was compared with the CL signal intensity obtained using the common serpentine chip design, with both approaches using at a total flow rate of 15 μl min -1 ; the results showed that the nanodroplets provided 600% higher CL signal intensity at this low flow rate. Using the optimum conditions, calibration equations, limits of detection (LOD) and limits of quantification (LOQ) for gallic acid (GA), caffeic acid (CA), kaempferol (KAM), quercetin (QRC) and catechin (CAT) were obtained. The LOD ranged from 6.2 ppb for CA to 11.0 ppb for QRC. Finally, the method was applied for the determination of TPC in several local and commercial honey samples. Copyright © 2018 John Wiley & Sons, Ltd.

Measurements of Oxychlorine species on Mars

NASA Astrophysics Data System (ADS)

Sutter, B.; Quinn, R. C.; Archer, P. D.; Glavin, D. P.; Glotch, T. D.; Kounaves, S. P.; Osterloo, M. M.; Rampe, E. B.; Ming, D. W.

2017-07-01

Mars landed and orbiter missions have instrumentation capable of detecting oxychlorine phases (e.g. perchlorate, chlorate) on the surface. Perchlorate (~0.6 wt%) was first detected by the Wet Chemistry Laboratory in the surface material at the Phoenix Mars Landing site. Subsequent analyses by the Thermal Evolved Gas Analyser aboard the same lander detected an oxygen release (~465°C) consistent with the thermal decomposition of perchlorate. Recent thermal analysis by the Mars Science Laboratory's Sample Analysis at Mars instrument has also indicated the presence of oxychlorine phases (up to 1.2 wt%) in Gale Crater materials. Despite being at detectable concentrations, the Chemistry and Mineralogy (CheMin) X-ray diffractometer has not detected oxychlorine phases. This suggests that Gale Crater oxychlorine may exist as poorly crystalline phases or that perchlorate/chlorate mixtures exist, so that individual oxychlorine concentrations are below CheMin detection limits (~1 wt%). Although not initially designed to detect oxychlorine phases, reinterpretation of Viking Gas Chromatography/Mass Spectrometer data also suggest that oxychlorine phases are present in the Viking surface materials. Remote near-infrared spectral analyses by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) instrument indicate that at least some martian recurring slope lineae (RSL) have spectral signatures consistent with the presence of hydrated perchlorates or chlorates during the seasons when RSL are most extensive. Despite the thermal emission spectrometer, Thermal Emission Imaging System, Observatoire pour la Minéralogie, l'Eau, les Glaces et l'Activité and CRISM detection of hundreds of anhydrous chloride (~10-25 vol%) deposits, expected associated oxychlorine phases (>5-10 vol%) have not been detected. Total Cl and oxychlorine data sets from the Phoenix Lander and the Mars Science Laboratory missions could be used to develop oxychlorine versus total Cl correlations, which may constrain oxychlorine concentrations at other locations on Mars by using total Cl determined by other missions (e.g. Viking, Pathfinder, MER and Odyssey). Development of microfluidic or `lab-on-a-chip' instrumentation has the potential to be the next generation analytical capability used to identify and quantify individual oxychlorine species on future landed robotic missions to Mars.

Quantification of MDMA and MDA in abusers' hair samples by semi-micro column HPLC with fluorescence detection.

PubMed

Nakamura, Shinichi; Tomita, Mamoru; Wada, Mitsuhiro; Chung, Heesun; Kuroda, Naotaka; Nakashima, Kenichiro

2006-01-01

A sensitive semi-micro column high-performance liquid chromatography with fluorescence detection method was developed for the determination of 3,4-methylenedioxymethamphetamine (MDMA), 3,4-methylenedioxyamphetamine (MDA), methamphetamine (MP) and amphetamine (AP) in human hair. 4-(4,5-Diphenyl-1H-imidazol-2-yl)benzoyl chloride (DIB-Cl) and 1-methyl-3-phenylpropylamine were used as labeling reagent and internal standard, respectively. These drugs were extracted from hair into 5% trifluoroacetic acid in methanol, and fluorescent labeled with DIB-Cl. The separation of DIB-derivatives was achieved on a reversed-phase semi-micro ODS column with an acetonitrile-methanol-water (30:40:30, v/v/v%) mixture as a mobile phase. The limits of detection at a signal-to-noise ratio of 3 for MDMA, MDA, MP and AP were 0.25, 0.15, 0.25 and 0.19 ng/mg, respectively. Precision of intra- and inter-day assay as the relative standard deviation were in the range 1.5-6.8% (n = 5) and 2.7-4.7% (n = 5), respectively. The proposed method was highly sensitive and able to detect MDMA and its related compounds in small amounts of hair sample, and could be applied to quantification of six abusers' hair samples. Copyright 2006 John Wiley & Sons, Ltd.

Determination of ampicillin sodium using the cupric oxide nanoparticles-luminol-H2 O2 chemiluminescence reaction.

PubMed

Iranifam, Mortaza; Kharameh, Merhnaz Khabbaz

2014-09-01

A simple and sensitive chemiluminescence (CL) method has been developed for the determination of ampicillin sodium at submicromolar levels. The method is based on the inhibitory effect of ampicillin sodium on the cupric oxide nanoparticles (CuO NPs)-luminol-H2 O2 CL reaction. Experimental parameters affecting CL inhibition including concentrations of CuO NPs, luminol, H2 O2 and NaOH were optimized. Under optimum conditions, the calibration plot was linear in the analyte concentration range 4.0 × 10(-7) -4.0 × 10(-6) mol/L. The limit of detection was 2.6 × 10(-7) mol/L and the relative standard deviation (RSD) for six replicate determinations of 1 × 10(-6) mol/L ampicillin sodium was 4.71%. Also, X-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis were employed to characterize the CuO NPs. The utility of the proposed method was demonstrated by determining ampicillin sodium in pharmaceutical preparation. Copyright © 2013 John Wiley & Sons, Ltd.

A method of chemiluminescence coupled with ultrafiltration for investigating the interaction between ibuprofen and human serum albumin.

PubMed

Xiong, Xunyu; Zhang, Qunzheng; Nan, Yefei; Gu, Xuefan

2013-01-01

In acidic media, ibuprofen substantially enhanced the weak chemiluminescence (CL) produced by sodium sulfite and potassium permanganate. The increased signals were linearly correlated with ibuprofen concentrations ranging from 1.2 × 10(-3) to 4.8 μM, with a detection limit of 4.8 × 10(-4) μM. Two ultrafiltration (UF) membranes were used to construct a unit for trapping 0.15 and 0.75 μM human serum albumin (HSA) and coupled online with the CL system. At low HSA concentrations, the numbers of bound molecules per binding site were calculated to be 0.9 for Sudlow site I and 6.2 for Sudlow site II. The association constants on these binding sites were 5.9 × 10(5) and 3.4 × 10(4) M(-1), respectively. Our CL-UF protocol presents a rapid and sensitive method for studies on drug-protein interaction. Copyright © 2012 John Wiley & Sons, Ltd.

Colorimetric and luminescent bifunctional iridium(III) complexes for the sensitive recognition of cyanide ions

NASA Astrophysics Data System (ADS)

Chen, Xiudan; Wang, Huili; Li, Jing; Hu, Wenqin; Li, Mei-Jin

2017-02-01

Two new cyclometalated iridium(III) complexes [(ppy)2Irppz]Cl (1) and [(ppy)2Irbppz]Cl (2) (where ppy = 2-phenylpyridine, ppz = 4,7-phenanthrolino-5,6:5,6-pyrazine, bppz = 2.3-di-2-pyridylpyrazine), were designed and synthesized. The structure of [(ppy)2Irppz]Cl was determined by single crystal X-ray diffraction. Their photophysical properties were also studied. This kind of complexes could coordinate with Cu2 +, the photoluminescence (PL) of the complex was quenched, and the color changed from orange-red to green. The forming M-Cu (M: complexes 1 and 2) ensemble could be further utilized as a colorimetric and emission ;turn-on; bifunctional detection for CN-, especially for complex 1-Cu2 + showed a high sensitivity toward CN- with a limit of diction is 97 nM. Importantly, this kind of iridium(III) complexes shows a unique recognition of cyanide ions over other anions which makes it an eligible sensing probe for cyanide ions.

Vitamin A determination in milk samples based on the luminol-periodate chemiluminescence system.

PubMed

Rishi, Lubna; Yaqoob, Mohammad; Waseem, Amir; Nabi, Abdul

2014-01-01

A simple and rapid flow injection (FI) method for the determination of retinyl acetate is reported based on its enhancing effect on the luminol-periodate chemiluminescence (CL) system in an alkaline medium. The detection limit (3s×blank) was 8.0×10⁻⁸ mol L⁻¹, with an injection throughput of 90 h⁻¹. The method allows linear increase of CL intensity over the retinyl acetate concentration range of 1.0-100×10⁻⁷ mol L⁻¹ (R²=0.9996) with relative standard deviations of 2.4% (n=10) for 5.0×10⁻⁷ mol L⁻¹. The key chemical and physical variables (reagent concentrations, flow rates, sample volume, and photomultiplier tube (PMT) voltage) were optimized and potential interferences were investigated. The method was successfully applied to human milk, fresh cow's milk and infant milk-based formulas and the results were in good agreement with the previously reported HPLC method. A brief discussion on the possible CL reaction mechanism is also presented.

Effect of Chorda Tympani Nerve Transection on Salt Taste Perception in Mice

PubMed Central

Ishiwatari, Yutaka; Theodorides, Maria L.; Bachmanov, Alexander A.

2011-01-01

Effects of gustatory nerve transection on salt taste have been studied extensively in rats and hamsters but have not been well explored in the mouse. We examined the effects of chorda tympani (CT) nerve transection on NaCl taste preferences and thresholds in outbred CD-1 mice using a high-throughput phenotyping method developed in our laboratory. To measure taste thresholds, mice were conditioned by oral self-administration of LiCl or NaCl and then presented with NaCl concentration series in 2-bottle preference tests. LiCl-conditioned and control NaCl-exposed mice were given bilateral transections of the CT nerve (LiCl-CTX, NaCl-CTX) or were left intact as controls (LiCl-CNT, NaCl-CNT). After recovery from surgery, mice received a concentration series of NaCl (0–300 mM) in 48-h 2-bottle tests. CT transection increased NaCl taste thresholds in LiCl-conditioned mice and eliminated avoidance of concentrated NaCl in control NaCl-exposed mice. This demonstrates that in mice, the CT nerve is important for detection and recognition of NaCl taste and is necessary for the normal avoidance of high concentrations of NaCl. The results of this experiment also show that the method of high-throughput phenotyping of salt taste thresholds is suitable for detecting changes in the taste periphery in mouse genetic studies. PMID:21743094

Coupling Molecular Beacons to Barcoded Metal Nanowires for Multiplexed, Sealed Chamber DNA Bioassays

PubMed Central

Stoermer, Rebecca L.; Cederquist, Kristin B.; McFarland, Sean K.; Sha, Michael Y.; Penn, Sharron G.

2010-01-01

We have combined molecular beacon (MB) probes with barcoded metal nanowires to enable no-wash, sealed chamber, multiplexed detection of nucleic acids. Probe design and experimental parameters important in nanowire-based MB assays are discussed. Loop regions of 24 bases and 5 base pair stem regions in the beacon probes gave optimal performance. Our results suggest that thermodynamic predictions for secondary structure stability of solution-phase MB can guide probe design for nanowire-based assays. Dengue virus-specific probes with predicted solution-phase ΔG of folding in 500 mM buffered NaCl of approximately −4 kcal/mol performed better than those with ΔG > −2 or < −6 kcal/mol. Buffered 300–500 mM NaCl was selected after comparison of several buffers previously reported for similar types of assays, and 200–500 mM NaCl was found to be the optimal ionic strength for the hybridization temperatures (25 and 50 °C) and probe designs used here. Target binding to the surface as a function of solution concentration fit a Sips isotherm with Kd = 1.7 ± 0.3 nM. The detection limit was ∼100 pM, limited by incomplete quenching. Single base mismatches could be discriminated from fully complementary targets. Oligonucleotide target sequences specific for human immunodeficiency, hepatitis C, and severe acute respiratory viruses were assayed simultaneously in a no-wash, sealed chamber, multiplexed experiment in which each of three probe sequences was attached to a different pattern of encoded nanowires. Finally, we demonstrated that probe-coated nanowires retain their selectivity and sensitivity in a triplexed assay after storage for over 3 months. PMID:17177440

Strategies for oxychlorine removal to facilitate pyrolytic organic matter analysis in subsurface oxychlorine-rich brines on Earth and Mars

NASA Astrophysics Data System (ADS)

Chou, L.; Kenig, F. P. H.; Jackson, W. A.

2017-12-01

The ubiquity of oxychlorine salts in the Martian soil significantly hampers our ability to unambiguously detect and characterize organic matter (OM) that is of Martian origin via pyrolysis. The Sample Analysis at Mars (SAM) instrument suite onboard the Curiosity Rover detected chlorinated and non-chlorinated inorganic and organic compounds (HCl, CO2, C1-C4 chloroalkanes, chlorobenzenes) at Gale Crater. The C1 to C3 chloroalkanes have been attributed to the reaction between the oxychlorines and OM deriving from the SAM instrument suite. Chlorobenzenes and dichloroalkanes, on the other hand, were observed at elevated levels at Gale Crater and are hypothesized to be the first indigenous OM detected on Mars. However, due to complex chlorination and oxidation reactions in the SAM pyrolysis oven, the precursor molecules to these chlorohydrocarbons are unknown. In order to facilitate the detection of OM in ClO4-rich samples on Mars, we explore various strategies, such as using strong base anion (SBA) exchange resins, to remove ClO4- from a Mars analog sample. This sample was obtained from a subsurface brine beneath the frozen Lake Vida (East Antarctica). Lake Vida brine (LVBr) contains abundant DOC at 48.2 mmol·L-1 and ClO4- at 49 µg•L-1. Resin-treated samples were analyzed via solid phase microextraction (SPME) gas chromatography-mass spectrometry (GC-MS). The SBA resin successfully removed ClO4- to below detection level from standard brine solution (3M NaCl + 50 µg•L-1 ClO4-) and LVBr using a minimum of 3.4 mL of resin volume per 100 mL of sample volume. Although the abundance of CO2, CH2Cl2 and HCl formed via the oxidation and chlorination of OM during SPME GC-MS analysis of resin-treated LVBr was significantly reduced, it was not completely eliminated. This suggests that the degradation of other oxychlorines (i.e. ClO3-) may also be obstructing our ability to detect OM indigenous to LVBr. The average level of ClO3- in LVBr after resin treatment was 16.7 ppb. We attempt to remove ClO3- using a nitrate-specific resin, as ClO3-specific resins are not currently manufactured, in an effort to further reduce the levels of ClO3- from the brine sample, allowing for the downstream pyrolytic analysis of OM present in LVBr, as well as oxychlorine-rich samples on Mars.

Dual-Readout Immunochromatographic Assay by Utilizing MnO 2 Nanoflowers as the Unique Colorimetric/Chemiluminescent Probe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ouyang, Hui; Lu, Qian; Wang, Wenwen

Manganese dioxide nanoflowers (MnO2 NFs) were synthesized and utilized as a dual readout probe to develop a novel immunochromatographic test strip (ITS) for detecting pesticide residues using chlorpyrifos as the model analyte. MnO2 NFs-labeled antibody for chlorpyrifos was employed as the signal tracer for conducting the ITS. After 10-min competitive immunoreaction, the tracer antibody was captured by the immobilized immunogen on test line in the test strip, resulting in the accumulation of MnO2 NFs. The accumulation of MnO2 NFs led to the appearance of brown color on the test line, which could be easily observed by the naked eye asmore » a qualitative readout. Moreover, MnO2 NFs showed a remarkably enhancing effect on the luminol-H2O2 chemiluminescent (CL) system. Unlike peroxidase-like nanomaterials, the enhancing mechanism of MnO2 NFs was based on its oxidant activity to decompose H2O2 for forming reactive oxygen species. After initiating the CL system in the test zone, strong CL signal was collected as a quantitative readout to sensitively detect chlorpyrifos. Under optimal conditions, the linear range of chlorpyrifos was 0.1–50 ng/mL with a low detection limit of 0.033 ng/mL (S/N = 3). The reliability of the dual-readout ITS was successfully demonstrated by the application on traditional Chinese medicine and environmental water samples. Due to the simultaneous rapid-qualitative and sensitive-quantitative detection, the dual-readout protocol provides a promising strategy for rapid screening and field assay on various areas such as environmental monitoring, food safety and point-of-care testing.« less

Assessment of Myeloperoxidase Activity by the Conversion of Hydroethidine to 2-Chloroethidium*

PubMed Central

Maghzal, Ghassan J.; Cergol, Katie M.; Shengule, Sudhir R.; Suarna, Cacang; Newington, Darren; Kettle, Anthony J.; Payne, Richard J.; Stocker, Roland

2014-01-01

Oxidants derived from myeloperoxidase (MPO) contribute to inflammatory diseases. In vivo MPO activity is commonly assessed by the accumulation of 3-chlorotyrosine (3-Cl-Tyr), although 3-Cl-Tyr is formed at low yield and is subject to metabolism. Here we show that MPO activity can be assessed using hydroethidine (HE), a probe commonly employed for the detection of superoxide. Using LC/MS/MS, 1H NMR, and two-dimensional NOESY, we identified 2-chloroethidium (2-Cl-E+) as a specific product when HE was exposed to hypochlorous acid (HOCl), chloramines, MPO/H2O2/chloride, and activated human neutrophils. The rate constant for HOCl-mediated conversion of HE to 2-Cl-E+ was estimated to be 1.5 × 105 m−1s−1. To investigate the utility of 2-Cl-E+ to assess MPO activity in vivo, HE was injected into wild-type and MPO-deficient (Mpo−/−) mice with established peritonitis or localized arterial inflammation, and tissue levels of 2-Cl-E+ and 3-Cl-Tyr were then determined by LC/MS/MS. In wild-type mice, 2-Cl-E+ and 3-Cl-Tyr were detected readily in the peritonitis model, whereas in the arterial inflammation model 2-Cl-E+ was present at comparatively lower concentrations (17 versus 0.3 pmol/mg of protein), and 3-Cl-Tyr could not be detected. Similar to the situation with 3-Cl-Tyr, tissue levels of 2-Cl-E+ were decreased substantially in Mpo−/− mice, indicative of the specificity of the assay. In the arterial inflammation model, 2-Cl-E+ was absent from non-inflamed arteries and blood, suggesting that HE oxidation occurred locally in the inflamed artery. Our data suggest that the conversion of exogenous HE to 2-Cl-E+ may be a useful selective and sensitive marker for MPO activity in addition to 3-Cl-Tyr. PMID:24436331

Carbon nanopipette electrodes for dopamine detection in Drosophila.

PubMed

Rees, Hillary R; Anderson, Sean E; Privman, Eve; Bau, Haim H; Venton, B Jill

2015-04-07

Small, robust, sensitive electrodes are desired for in vivo neurotransmitter measurements. Carbon nanopipettes have been previously manufactured and used for single-cell drug delivery and electrophysiological measurements. Here, a modified fabrication procedure was developed to produce batches of solid carbon nanopipette electrodes (CNPEs) with ∼250 nm diameter tips, and controllable lengths of exposed carbon, ranging from 5 to 175 μm. The electrochemical properties of CNPEs were characterized with fast-scan cyclic voltammetry (FSCV) for the first time. CNPEs were used to detect the electroactive neurotransmitters dopamine, serotonin, and octopamine. CNPEs were significantly more sensitive for serotonin detection than traditional carbon-fiber microelectrodes (CFMEs). Similar to CFMEs, CNPEs have a linear response for dopamine concentrations ranging from 0.1 to 10 μM and a limit of detection of 25 ± 5 nM. Recordings with CNPEs were stable for over 3 h when the applied triangle waveform was scanned between -0.4 and +1.3 V vs Ag/AgCl/Cl(-) at 400 V/s. CNPEs were used to detect endogenous dopamine release in Drosophila larvae using optogenetics, which verified the utility of CNPEs for in vivo neuroscience studies. CNPEs are advantageous because they are 1 order of magnitude smaller in diameter than typical CFMEs and have a sharp, tunable geometry that facilitates penetration and implantation for localized measurements in distinct regions of small organisms, such as the Drosophila brain.

A Cr(VI) selective probe based on a quinoline-amide calix[4]arene

NASA Astrophysics Data System (ADS)

Ferreira, Juliane F.; Bagatin, Izilda A.

2018-01-01

A new quinoline-amide calix[4]arene 3-receptor for detection of hazardous anions and cations have been synthesized. The 3-receptor was examined for its sensing properties towards several different anions (Cr2O72 -, SCN-, F-, Cl-, NO3-) and metal ions (Hg2+, Cd2+, Ag+) by UV-vis and fluorescence spectroscopies. It was detected that the 3-receptor has only sensing ability for Cr2O72 - and Hg2+ ions, resulting in the association constants higher for Cr2O72 - than to the Hg2+ ions. High selectivity towards Cr2O72 - were also observed by fluorescence measurement among other ions (F-, Cl-, SCN-, Hg2+, Cd2+, Ag+) with a low limit of detection (7.36 × 10-6 mol dm-3). Proton NMR anion-binding investigations revealed a strong interaction of Cr2O72 - anion with NH and CH groups of the receptor, showing that the combination with hydrogen-bonds donor groups strengthened the anion receptor association. Furthermore, remarkable association constants for dichromate anion obtained by all techniques strongly suggest the 3-receptor as a selective Cr(VI) sensor.

Amperometric detection of glucose in fruit juices with polypyrrole-based biosensor with an integrated permselective layer for exclusion of interferences.

PubMed

Ayenimo, Joseph G; Adeloju, Samuel B

2017-08-15

A novel polypyrrole (PPy)-based bilayer amperometric glucose biosensor integrated with a permselective layer has been developed for detection of glucose in the presence of interferences. It comprises of a PPy-GOx film grown, in the absence of electrolyte, as an inner layer, and a permselective PPy-Cl film as an outer layer. The PPy-GOx/PPy-Cl bilayer biosensor was effective in rejecting 98% of ascorbic acid and 100% of glycine, glutamic acid and uric acid. With an outer layer thickness of 6.6nm, the bilayer biosensor gave nearly identical glucose response to that of a single layer PPy-GOx biosensor. The biosensor also exhibited good reproducibility (1.9% rsd, n=10), high stability (more than 2months), wide linear range (0.5-24mM), low K m (8.4mM), high I max (77.2μAcm -2 ), low detection limit (26.9μM) and good sensitivity (3.5μAcm -2 mM -1 ). The bilayer biosensor was successfully employed for glucose determination in various fruit juices. Copyright © 2017 Elsevier Ltd. All rights reserved.

A Cr(VI) selective probe based on a quinoline-amide calix[4]arene.

PubMed

Ferreira, Juliane F; Bagatin, Izilda A

2018-01-15

A new quinoline-amide calix[4]arene 3-receptor for detection of hazardous anions and cations have been synthesized. The 3-receptor was examined for its sensing properties towards several different anions (Cr 2 O 7 2- , SCN - , F - , Cl - , NO 3 - ) and metal ions (Hg 2+ , Cd 2+ , Ag + ) by UV-vis and fluorescence spectroscopies. It was detected that the 3-receptor has only sensing ability for Cr 2 O 7 2- and Hg 2+ ions, resulting in the association constants higher for Cr 2 O 7 2- than to the Hg 2+ ions. High selectivity towards Cr 2 O 7 2- were also observed by fluorescence measurement among other ions (F - , Cl - , SCN - , Hg 2+ , Cd 2+ , Ag + ) with a low limit of detection (7.36×10 -6 moldm -3 ). Proton NMR anion-binding investigations revealed a strong interaction of Cr 2 O 7 2- anion with NH and CH groups of the receptor, showing that the combination with hydrogen-bonds donor groups strengthened the anion receptor association. Furthermore, remarkable association constants for dichromate anion obtained by all techniques strongly suggest the 3-receptor as a selective Cr(VI) sensor. Copyright © 2017 Elsevier B.V. All rights reserved.

Peroxyoxalate chemiluminescence detection for the highly sensitive determination of fluorescence-labeled chlorpheniramine with Suzuki coupling reaction.

PubMed

Adutwum, Lawrence Asamoah; Kishikawa, Naoya; Ohyama, Kaname; Harada, Shiro; Nakashima, Kenichiro; Kuroda, Naotaka

2010-09-01

A sensitive and selective high performance liquid chromatography-peroxyoxalate chemiluminescence (PO-CL) method has been developed for the simultaneous determination of chlorpheniramine (CPA) and monodesmethyl chlorpheniramine (MDCPA) in human serum. The method combines fluorescent labeling with 4-(4,5-diphenyl-1H-imidazole-2-yl)phenyl boronic acid using Suzuki coupling reaction with PO-CL detection. CPA and MDCPA were extracted from human serum by liquid-liquid extraction with n-hexane. Excess labeling reagent, which interfered with trace level determination of analytes, was removed by solid-phase extraction using a C18 cartridge. Separation of derivatives of both analytes was achieved isocratically on a silica column with a mixture of acetonitrile and 60 mM imidazole-HNO(3) buffer (pH 7.2; 85:15, v/v) containing 0.015% triethylamine. The proposed method exhibited a good linearity with a correlation coefficient of 0.999 for CPA and MDCPA within the concentration range of 0.5-100 ng/mL. The limits of detection (S/N = 3) were 0.14 and 0.16 ng/mL for CPA and MDCPA, respectively. Using the proposed method, CPA could be selectively determined in human serum after oral administration.

Manual-slide-engaged paper chip for parallel SERS-immunoassay measurement of clenbuterol from swine hair.

PubMed

Zheng, Tingting; Gao, Zhigang; Luo, Yong; Liu, Xianming; Zhao, Weijie; Lin, Bingcheng

2016-02-01

Clenbuterol (CL), as a feed additive, has been banned in many countries due to its potential threat to human health. In detection of CL, a fast, low-cost technique with high accuracy and specificity would be ideal for its administrative on-field inspections. Among the attempts to pursue a reliable detection tool of CL, a technique that combines surface enhanced Raman spectroscopy (SERS) and immunoassay, is close to meet the requirements as above. However, multiple steps of interactions between CL analyte, antibody, and antigen are involved in this method, and under conventional setup, the operation of SERS/immunoassay were unwieldy. In this paper, to facilitate a more manageable sample manipulation for SERS-immunoassay measurement, a 3D paper chip was suggested. A switch-on-chip multilayered (abbreviated as SoCM-) microfluidic paper-based analysis device (μPad) was fabricated to provide operators with manual switches on the interactions between different microfluids. Besides, on a detection slip we made on the main body of our SoCM-μPad, antigen was anchored in pattern. With this architecture, multistep interactions between the CL analyte in swine hair extract and the SERS probe-modified antibody and antigen, were managed for on-chip SERS-immunoassay detection. This would be very attractive for fast, cheap, accurate, and on-site specific detection of CL from real samples. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Search for one large extra dimension with the DELPHI detector at LEP

NASA Astrophysics Data System (ADS)

Abdallah, J.; Abreu, P.; Adam, W.; Adzic, P.; Albrecht, T.; Alemany-Fernandez, R.; Allmendinger, T.; Allport, P. P.; Amaldi, U.; Amapane, N.; Amato, S.; Anashkin, E.; Andreazza, A.; Andringa, S.; Anjos, N.; Antilogus, P.; Apel, W.-D.; Arnoud, Y.; Ask, S.; Asman, B.; Augustin, J. E.; Augustinus, A.; Baillon, P.; Ballestrero, A.; Bambade, P.; Barbier, R.; Bardin, D.; Barker, G. J.; Baroncelli, A.; Battaglia, M.; Baubillier, M.; Becks, K.-H.; Begalli, M.; Behrmann, A.; Ben-Haim, E.; Benekos, N.; Benvenuti, A.; Berat, C.; Berggren, M.; Bertrand, D.; Besancon, M.; Besson, N.; Bloch, D.; Blom, M.; Bluj, M.; Bonesini, M.; Boonekamp, M.; Booth, P. S. L.; Borisov, G.; Botner, O.; Bouquet, B.; Bowcock, T. J. V.; Boyko, I.; Bracko, M.; Brenner, R.; Brodet, E.; Bruckman, P.; Brunet, J. M.; Buschbeck, B.; Buschmann, P.; Calvi, M.; Camporesi, T.; Canale, V.; Carena, F.; Castro, N.; Cavallo, F.; Chapkin, M.; Charpentier, Ph.; Checchia, P.; Chierici, R.; Chliapnikov, P.; Chudoba, J.; Chung, S. U.; Cieslik, K.; Collins, P.; Contri, R.; Cosme, G.; Cossutti, F.; Costa, M. J.; Crennell, D.; Cuevas, J.; D'Hondt, J.; da Silva, T.; da Silva, W.; Della Ricca, G.; de Angelis, A.; de Boer, W.; de Clercq, C.; de Lotto, B.; de Maria, N.; de Min, A.; de Paula, L.; di Ciaccio, L.; di Simone, A.; Doroba, K.; Drees, J.; Eigen, G.; Ekelof, T.; Ellert, M.; Elsing, M.; Espirito Santo, M. C.; Fanourakis, G.; Fassouliotis, D.; Feindt, M.; Fernandez, J.; Ferrer, A.; Ferro, F.; Flagmeyer, U.; Foeth, H.; Fokitis, E.; Fulda-Quenzer, F.; Fuster, J.; Gandelman, M.; Garcia, C.; Gavillet, Ph.; Gazis, E.; Gokieli, R.; Golob, B.; Gomez-Ceballos, G.; Goncalves, P.; Graziani, E.; Grosdidier, G.; Grzelak, K.; Guy, J.; Haag, C.; Hallgren, A.; Hamacher, K.; Hamilton, K.; Haug, S.; Hauler, F.; Hedberg, V.; Hennecke, M.; Hoffman, J.; Holmgren, S.-O.; Holt, P. J.; Houlden, M. A.; Jackson, J. N.; Jarlskog, G.; Jarry, P.; Jeans, D.; Johansson, E. K.; Jonsson, P.; Joram, C.; Jungermann, L.; Kapusta, F.; Katsanevas, S.; Katsoufis, E.; Kernel, G.; Kersevan, B. P.; Kerzel, U.; King, B. T.; Kjaer, N. J.; Kluit, P.; Kokkinias, P.; Kourkoumelis, C.; Kouznetsov, O.; Krumstein, Z.; Kucharczyk, M.; Lamsa, J.; Leder, G.; Ledroit, F.; Leinonen, L.; Leitner, R.; Lemonne, J.; Lepeltier, V.; Lesiak, T.; Liebig, W.; Liko, D.; Lipniacka, A.; Lopes, J. H.; Lopez, J. M.; Loukas, D.; Lutz, P.; Lyons, L.; MacNaughton, J.; Malek, A.; Maltezos, S.; Mandl, F.; Marco, J.; Marco, R.; Marechal, B.; Margoni, M.; Marin, J.-C.; Mariotti, C.; Markou, A.; Martinez-Rivero, C.; Masik, J.; Mastroyiannopoulos, N.; Matorras, F.; Matteuzzi, C.; Mazzucato, F.; Mazzucato, M.; McNulty, R.; Meroni, C.; Migliore, E.; Mitaroff, W.; Mjoernmark, U.; Moa, T.; Moch, M.; Moenig, K.; Monge, R.; Montenegro, J.; Moraes, D.; Moreno, S.; Morettini, P.; Mueller, U.; Muenich, K.; Mulders, M.; Mundim, L.; Murray, W.; Muryn, B.; Myatt, G.; Myklebust, T.; Nassiakou, M.; Navarria, F.; Nawrocki, K.; Nemecek, S.; Nicolaidou, R.; Nikolenko, M.; Oblakowska-Mucha, A.; Obraztsov, V.; Olshevski, A.; Onofre, A.; Orava, R.; Osterberg, K.; Ouraou, A.; Oyanguren, A.; Paganoni, M.; Paiano, S.; Palacios, J. P.; Palka, H.; Papadopoulou, Th. D.; Pape, L.; Parkes, C.; Parodi, F.; Parzefall, U.; Passeri, A.; Passon, O.; Peralta, L.; Perepelitsa, V.; Perrotta, A.; Petrolini, A.; Piedra, J.; Pieri, L.; Pierre, F.; Pimenta, M.; Piotto, E.; Podobnik, T.; Poireau, V.; Pol, M. E.; Polok, G.; Pozdniakov, V.; Pukhaeva, N.; Pullia, A.; Radojicic, D.; Rebecchi, P.; Rehn, J.; Reid, D.; Reinhardt, R.; Renton, P.; Richard, F.; Ridky, J.; Rivero, M.; Rodriguez, D.; Romero, A.; Ronchese, P.; Roudeau, P.; Rovelli, T.; Ruhlmann-Kleider, V.; Ryabtchikov, D.; Sadovsky, A.; Salmi, L.; Salt, J.; Sander, C.; Savoy-Navarro, A.; Schwickerath, U.; Sekulin, R.; Siebel, M.; Sisakian, A.; Smadja, G.; Smirnova, O.; Sokolov, A.; Sopczak, A.; Sosnowski, R.; Spassov, T.; Stanitzki, M.; Stocchi, A.; Strauss, J.; Stugu, B.; Szczekowski, M.; Szeptycka, M.; Szumlak, T.; Tabarelli, T.; Tegenfeldt, F.; Timmermans, J.; Tkatchev, L.; Tobin, M.; Todorovova, S.; Tome, B.; Tonazzo, A.; Tortosa, P.; Travnicek, P.; Treille, D.; Tristram, G.; Trochimczuk, M.; Troncon, C.; Turluer, M.-L.; Tyapkin, I. A.; Tyapkin, P.; Tzamarias, S.; Uvarov, V.; Valenti, G.; van Dam, P.; van Eldik, J.; van Remortel, N.; van Vulpen, I.; Vegni, G.; Veloso, F.; Venus, W.; Verdier, P.; Verzi, V.; Vilanova, D.; Vitale, L.; Vrba, V.; Wahlen, H.; Washbrook, A. J.; Weiser, C.; Wicke, D.; Wickens, J.; Wilkinson, G.; Winter, M.; Witek, M.; Yushchenko, O.; Zalewska, A.; Zalewski, P.; Zavrtanik, D.; Zhuravlov, V.; Zimin, N. I.; Zintchenko, A.; Zupan, M.

2009-03-01

Single photons detected by the DELPHI experiment at LEP2 in the years 1997-2000 are reanalysed to investigate the existence of a single extra dimension in a modified ADD scenario with slightly warped large extra dimensions. The data collected at centre-of-mass energies between 180 and 209 GeV for an integrated luminosity of ˜650 pb-1 agree with the predictions of the Standard Model and allow a limit to be set on graviton emission in one large extra dimension. The limit obtained on the fundamental mass scale M D is 1.69 TeV/ c 2 at 95% CL, with an expected limit of 1.71 TeV/ c 2.

Selective Isobar Suppression for Accelerator Mass Spectrometry and Radioactive Ion Beam Science

DOE Office of Scientific and Technical Information (OSTI.GOV)

Galindo-Uribarri, Alfredo; Havener, Charles C; Lewis, Thomas L.

2010-01-01

Several applications of AMS will benefit from pushing further the detection limits of AMS isotopes. A new method of selective isobar suppression by photodetachment in a radio-frequency quadrupole ion cooler is being developed at HRIBF with a two-fold purpose: (1) increasing the AMS sensitivity for certain isotopes of interest and (2) purifying radioactive ion beams for nuclear science. The potential of suppressing the 36S contaminants in a 36Cl beam using this method has been explored with stable S- and Cl- ions and a Nd:YLF laser. In the study, the laser beam was directed along the experiment's beam line and throughmore » a RF quadrupole ion cooler. Negative 32S and 35Cl ions produced by a Cs sputter ion source were focused into the ion cooler where they were slowed by collisions with He buffer gas; this increased the interaction time between the negative ion beam and the laser beam. As a result, suppression of S- by a factor of 3000 was obtained with about 2.5 W average laser power in the cooler while no reduction in Cl- current was observed.« less

Evaluating evidence for Cl sources and oxidation chemistry in a coastal, urban environment

NASA Astrophysics Data System (ADS)

Young, C. J.; Washenfelder, R. A.; Edwards, P. M.; Parrish, D. D.; Gilman, J. B.; Kuster, W. C.; Mielke, L. H.; Osthoff, H. D.; Tsai, C.; Pikelnaya, O.; Stutz, J.; Veres, P. R.; Roberts, J. M.; Griffith, S.; Dusanter, S.; Stevens, P. S.; Flynn, J.; Grossberg, N.; Lefer, B.; Holloway, J. S.; Peischl, J.; Ryerson, T. B.; Atlas, E. L.; Blake, D. R.; Brown, S. S.

2013-05-01

The role of chlorine atoms (Cl) in atmospheric oxidation was traditionally thought to be limited to the marine boundary layer, where they are produced through heterogeneous reactions involving sea salt. However, recent observation of photolytic Cl precursors (ClNO2 and Cl2) formed from anthropogenic pollution has expanded the potential importance of Cl to include coastal and continental urban areas. Measurements of ClNO2 in Los Angeles during CalNex showed it to be an important primary (first generation) radical source. Ratios of volatile organic compounds (VOCs) have been proposed as a sensitive method to quantify Cl oxidation, but have shown little evidence for a significant role of Cl outside of the Arctic. We used a box model with the Master Chemical Mechanism (MCM v3.2) chemistry scheme, constrained by observations in Los Angeles, to examine the Cl-sensitivity of the most commonly used VOC ratios (i-butane, n-butane, and propane) as a function of NOx and secondary radical production. Model results indicated these and faster reacting VOC tracer ratios could not detect the influence of Cl unless the sustained ratio of OH to Cl was below 200. However, the model results also show that secondary (second generation) OH production resulting from Cl oxidation of VOCs is strongly influenced by NOx, and that this effect can obscure the importance of Cl as a primary oxidant. Calculated concentrations of Cl showed a maximum in mid-morning due to a photolytic source from ClNO2 and loss primarily to reactions with VOCs. The OH to Cl ratio was below 200 for approximately three hours in the morning, but Cl oxidation was not evident from the measured ratios of VOCs. Instead, model simulations show that secondary OH production causes VOC ratios to follow the values expected for OH oxidation despite the significant input of primary Cl from ClNO2 photolysis in the morning. Despite the prevalence of secondary OH as an oxidant in Los Angeles, Cl may play an important role in tropospheric chemistry. The reactivity of Cl in Los Angeles during CalNex was more than an order of magnitude larger than that of OH. In addition, because of its reactivity toward different classes of VOCs and its greater propensity to participate in chain propagation rather than sink reactions, Cl atoms have a different impact on regional atmospheric oxidation than do OH radicals.

The Nitrate/Perchlorate Ratio on Mars As an Indicator for Habitability

NASA Astrophysics Data System (ADS)

Stern, J. C.; Sutter, B.; McKay, C. P.; Navarro-Gonzalez, R.; Freissinet, C.; Conrad, P. G.; Mahaffy, P. R.; Archer, P. D., Jr.; Ming, D. W.; Martín-Torres, J.; Zorzano, M. P.

2014-12-01

Discovery of indigenous martian nitrogen in Mars surface materials has important implications for habitability and the potential development of a nitrogen cycle at some point in martian history. The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) Curiosity Rover detected evolved nitric oxide (NO) gas during pyrolysis of scooped aeolian sediments and drilled mudstone acquired in Gale Crater. The detection of NO suggests an indigenous source of fixed nitrogen, and may indicate a mineralogical sink for atmospheric N2 in the form of nitrate. The ratio of nitrate to oxychlorine species (e.g. perchlorate) may provide insight into the extent of development of a nitrogen cycle on Mars. Nitrate and perchlorate on Earth are geochemically related in arid environments such as the Atacama Desert and the Dry Valleys of Antarctica due to their similar mobilities and deposition mechanisms [1,2]. Here, low NO3-/ClO4- molar ratios (~1000) dominate, in comparison to other places on Earth, where the main nitrate source is biological fixation of N2 to NO3-, and there is no corresponding biological source of perchlorate, resulting in much higher NO3-/ClO4- molar ratios (~10,000). The NO3-/ClO4- molar ratio is estimated to be ~ 0.05 on Mars based on SAM measurements at Gale Crater [3]. The possibility exists that perchlorate brines could leach and increase nitrate concentrations at depth, increasing the martian NO3-/ClO4- ratio in the subsurface. However, it is unknown whether terrestrial NO3-/ClO4- molar ratios could be achieved by this mechanism. Nevertheless, the low NO3-/ClO4- the ratio detected by SAM suggests that N fixation to nitrate on Mars, whether biologically mediated or abiotic, was extremely limited compared to the potentially ongoing abiotic formation and deposition of oxychlorine species on the martian surface. [1] Kounaves, S.P. et al. "Discovery of natural perchlorate in the Antarctic dry valleys and its global implications." ES&T44, no. 7 (2010): 2360-2364. [2] Lybrand, R.A., et al. "The geochemical associations of nitrate and naturally formed perchlorate in the Mojave Desert, California, USA." GCA104 (2013): 136-147. [3] Ming, D. W. et al. "Volatile and organic compositions of sedimentary rocks in Yellowknife Bay, Gale crater, Mars." Science 343, no. 6169 (2014): 1245267.

Biodegradation kinetics of the nitramine explosive CL-20 in soil and microbial cultures.

PubMed

Panikov, N S; Sizova, M V; Ros, D; Christodoulatos, C; Balas, W; Nicolich, S

2007-06-01

The cyclic nitramine explosive CL-20 (C(6)H(6)N(12)O(12), 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12 -hexaazaisowurtzitane) is a relatively new energetic compound which could be a persistent organic pollutant. To follow its biodegradation dynamics, CL-20 was added to soil alone or together with organic co-substrates and N-source and incubated under oxic and anoxic conditions. Without co-substrates, the CL-20 degradation was detectable only under anoxic conditions. The highest degradation rate was found under aerobic conditions and with the addition of co-substrates, succinate and pyruvate being more efficient than acetate, glucose, starch or yeast extract. When added to intact soil, CL-20 degradation was not affected by the N content, but in soil serially diluted with N-free succinate-mineral medium, the process became N-limited. About 40% of randomly selected bacterial colonies grown on succinate agar medium were able to decompose CL-20. Based on 16S rDNA gene sequence and cell morphology, they were affiliated to Pseudomonas, Rhodococcus, Ochrobactrum, Mycobacterium and Ralstonia. In the pure culture of Pseudomonas sp. MS-P grown on the succinate-mineral N(+) medium, the degradation kinetics were first order with the same apparent kinetic constant throughout growth and decline phases of the batch culture. The observed kinetics agreed with the model that supposes co-metabolic transformation of CL-20 uncoupled from cell growth, which can be carried out by several constitutive cellular enzymes with wide substrate specificity.

Chemiluminescence of nitrogen-rich quantum dots in diperiodatoargentate(III) solution and its application in ferulic acid analysis.

PubMed

Fu, Zhaofu; Li, Gongke; Hu, Yufei

2016-12-01

A novel chemiluminescence (CL) system based on the reaction of fluorescent water-soluble nitrogen-rich quantum dots (N-dots) and diperiodatoargentate(III) (DPA) was developed. The prepared N-dots have a small size (≤10 nm) and high percentage of nitrogen (39.9 %), which exceeds the content of carbon in the same N-dots. The N-dots exhibit characteristic blue fluorescence under UV light and up-conversion luminescence. The relatively intense CL emission is based on the direct oxidation of N-dots by DPA. The CL emission may be attributed to the high nitrogen content and the special structure of the N-dots. The CL mechanism of N-dots and DPA was investigated by using CL, UV-Vis absorption, IR, fluorescence, and radical scavenging experiments. This investigation provides a way to study the optical properties of N-dots. The analytical applicability of the N-dots and DPA CL system in the determination of ferulic acid (FA) was explored. The CL intensity was linearly proportional to the concentration of ferulic acid from 3.0 × 10 -7 to 1.0 × 10 -5 g mL -1 with a detection limit of 8.0 × 10 -8 g mL -1 (3σ); the relative standard deviation was 2.4 % for 4.0 × 10 -7 g mL -1 FA (n = 9). The proposed method was successfully applied to the determination of ferulic acid in Angelica sinensis. The study provides valuable insight into the role of nitrogen-rich quantum dots in CL.

A simple method for the determination of glyphosate and aminomethylphosphonic acid in seawater matrix with high performance liquid chromatography and fluorescence detection.

PubMed

Wang, Shu; Liu, Baomin; Yuan, Dongxing; Ma, Jian

2016-12-01

Glyphosate (GLYP) is an important herbicide which is also used as the phosphorus source for marine organisms. The wide applications of GLYP can lead to its accumulation in oceans and coastal waters, thus creating environmental issues. However, there is limited methods for detection of GLYP and its degradation product, aminomethylphosphonic acid (AMPA) in saline samples. Therefore, a simple and fast method for the quantification of GLYP and AMPA in seawater matrix has been developed based on the derivatization with 9-fluorenylmethylchloroformate (FMOC-Cl), separation with high performance liquid chromatography (HPLC) and detection with fluorescence detector (FLD). In order to maximize sensitivity, the derivatization procedure was carefully optimized regarding concentration of FMOC-Cl, volume of borate buffer, pH of borate buffer, mixing and derivatization time. The derivatization reaction could be completed within 30min in seawater samples without any additional clean-up or desalting steps. Under the optimized conditions, the developed HPLC method showed a wide linear response (up to several mg/L, R 2 >0.99). The limits of detection were 0.60μg/L and 0.30μg/L for GLYP and AMPA in seawater matrix, respectively. The relative standard deviation was 14.0% for GLYP (1.00mg/L) and 3.1% for AMPA (100μg/L) in saline samples with three different operators (n=24). This method was applied to determine the concentration of GLYP and AMPA in seawater culture media and the recovery data indicated minimal matrix interference. Due to its simplicity, high reproducibility and successful application in seawater culture media analysis, this method is a potentially useful analytical technique for both marine research and environmental science. Copyright © 2016 Elsevier B.V. All rights reserved.

The Role of Chloride Complexation on Anaerobic and Aerobic Mercury Bioavailability

NASA Astrophysics Data System (ADS)

Stenzler, B.; Ruuskanen, M.; Hinz, A.; Poulain, A.

2016-12-01

In the absence of dissolved organic matter, chloride and sulphide are the dominant complexing agents affecting mercury (Hg) speciation in the environment. Bioreporters are good tools in evaluating bioavailable species of Hg. However, signal production for current Hg bioreporters requires oxygen, namely for lux and gfp gene encoded proteins, resulting in a paucity of data in anaerobic bioavailability of Hg species where it is methylated to toxic CH3Hg+. We developed and optimized a whole-cell Hg bioreporter using Escherichia coli 5α capable of functioning in aerobic and anaerobic conditions by transforming a vector containing the gene fusion between the regulatory circuitry of the mer-operon and a flavin mononucleotide-based fluorescent protein. The bioreporter exhibited no physiological limitations with respect to signal production over a chloride gradient ranging from 0 to 0.7 M. The bioreporter had a detection limit of 1 nM Hg(II) however we used 5nM Hg(II) as the optimal working concentration for Hg speciation assays. We report that HgCl42- is highly bioavailable under anoxic conditions in contrast to what was observed under oxic conditions where Hg was not bioavailable. HgCl3- was not bioavailable regardless of the presence of oxygen which we attributed to either coordination polymers consisting of [HgCl3-]x chains on the cell surface or molecular mimicry of HgCl42- onto anaerobically expressed periplasmic binding proteins specific for divalent polyatomic anions shuttling Hg to the inner membrane. In the presence of HgCl42- in saline media and Hg(OH)2 in non-saline media the addition of 2.5 and 5 μM Zn, respectively, completely inhibited uptake of neutral and negatively charged Hg species regardless of the presence of oxygen. The presence of S2- inhibited Hg uptake regardless of the presence or absence of chloride. Our experiments also suggest that ligand exchange occurred faster between S2- and Cl- than between S2- and OH-. The unexpected bioavailability of HgCl42- indicates the possibility of a novel mechanism for Hg uptake in marine environments while the bioavailability of HgS species is dependent on equilibration time and salinity.

Chlorine as a primary radical: evaluation of methods to understand its role in initiation of oxidative cycles

NASA Astrophysics Data System (ADS)

Young, C. J.; Washenfelder, R. A.; Edwards, P. M.; Parrish, D. D.; Gilman, J. B.; Kuster, W. C.; Mielke, L. H.; Osthoff, H. D.; Tsai, C.; Pikelnaya, O.; Stutz, J.; Veres, P. R.; Roberts, J. M.; Griffith, S.; Dusanter, S.; Stevens, P. S.; Flynn, J.; Grossberg, N.; Lefer, B.; Holloway, J. S.; Peischl, J.; Ryerson, T. B.; Atlas, E. L.; Blake, D. R.; Brown, S. S.

2014-04-01

The role of chlorine atoms (Cl) in atmospheric oxidation has been traditionally thought to be limited to the marine boundary layer, where they are produced through heterogeneous reactions involving sea salt. However, recent observation of photolytic Cl precursors (ClNO2 and Cl2) formed from anthropogenic pollution has expanded the potential importance of Cl to include coastal and continental urban areas. Measurements of ClNO2 in Los Angeles during CalNex (California Nexus - Research at the Nexus of Air Quality and Climate Change) showed it to be an important primary (first generation) radical source. Evolution of ratios of volatile organic compounds (VOCs) has been proposed as a method to quantify Cl oxidation, but we find no evidence from this approach for a significant role of Cl oxidation in Los Angeles. We use a box model with the Master Chemical Mechanism (MCM v3.2) chemistry scheme, constrained by observations in Los Angeles, to examine the Cl sensitivity of commonly used VOC ratios as a function of NOx and secondary radical production. Model results indicate VOC tracer ratios could not detect the influence of Cl unless the ratio of [OH] to [Cl] was less than 200 for at least a day. However, the model results also show that secondary (second generation) OH production resulting from Cl oxidation of VOCs is strongly influenced by NOx, and that this effect obscures the importance of Cl as a primary oxidant. Calculated concentrations of Cl showed a maximum in mid-morning due to a photolytic source from ClNO2 and loss primarily to reactions with VOCs. The [OH] to [Cl] ratio was below 200 for approximately 3 h in the morning, but Cl oxidation was not evident from the measured ratios of VOCs. Instead, model simulations show that secondary OH production causes VOC ratio evolution to follow that expected for OH oxidation, despite the significant input of primary Cl from ClNO2 photolysis in the morning. Even though OH is by far the dominant oxidant in Los Angeles, Cl atoms do play an important role in photochemistry there, constituting 9% of the primary radical source. Furthermore, Cl-VOC reactivity differs from that of OH, being more than an order of magnitude larger and dominated by VOCs, such as alkanes, that are less reactive toward OH. Primary Cl is also slightly more effective as a radical source than primary OH due to its greater propensity to initiate radical propagation chains via VOC reactions relative to chain termination via reaction with nitrogen oxides.

Combined Treatment on the Inactivation of Naturally Existing Bacteria and Escherichia coli O157:H7 Inoculated on Fresh-Cut Kale.

PubMed

Kang, Ji Hoon; Song, Kyung Bin

2017-02-28

An aqueous chlorine dioxide (ClO₂) treatment combined with highly activated calcium oxide (CaO) and mild heat was tested for inactivating naturally existing bacteria and Escherichia coli O157:H7 inoculated on fresh-cut kale. Kale samples were treated with different concentrations of ClO₂ (10, 30, and 50 ppm), CaO (0.01%, 0.05%, 0.1%, and 0.2%), and mild heat (25°C, 45°C, 55°C, and 65°C) as well with combinations of 30 or 50 ppm ClO₂ and 0.2% CaO at 55°C for 3 min. An increasing concentration of ClO₂ and CaO significantly reduced the microbialpopulation compared with the control. In addition, mild heating at 55°C elicited greater microbial reduction than the other temperatures. A combined treatment of 50 ppm ClO₂ and 0.2% CaO at 55°C reduced the population of naturally existing bacteria on kale by 3.10 logcolony forming units (CFU)/g, and the counts of E. coli O157:H7 were below the detection limit (1 log CFU/g). In addition, no significant differences in the Hunter color values were evident in any treatment during storage. Therefore, a combined treatment of ClO₂ and active CaO at 55°C can be an effective sanitizing method to improve the microbiological safety of fresh-cut kale without affecting its quality.

Revealing interaction between sulfobutylether-β-cyclodextrin and reserpine by chemiluminescence and site-directed molecular docking.

PubMed

Xiong, Xunyu; Wu, Min; Zhao, Xinfeng; Song, Zhenghua

2014-09-01

The host-guest interaction between sulfobutylether-β-cyclodextrin (SBE-β-CD) and reserpine (RSP) is described using flow injection-chemiluminescence (FI-CL) and site-directed molecular docking methods. It was found that RSP could inhibit the CL intensity produced by a luminol/SBE-β-CD system. The decrease in CL intensity was logarithmic over an RSP concentration range of 0.03 to 700.0 nM, giving a regression equation of ∆I = 107.1lgCRES  + 186.1 with a detection limit of 10 pM (3σ). The CL assay was successfully applied in the determination of RSP in injection, saliva and urine samples with recoveries in the range 93.5-106.1%. Using the proposed CL model, the binding constant (KCD-R ) and the stoichiometric ratio of SBE-β-CD/RSP were calculated to be 7.4 × 10(6)  M(-1) and 1 : 1, respectively. Using molecular docking, it was confirmed that luminol binds to the small cavity of SBE-β-CD with a nonpolar interaction, while RSP targeted the larger cavity of SBE-β-CD and formed a 1 : 1 complex with hydrogen bonds. The proposed new CL method has the potential to become a powerful tool for revealing the host-guest interaction between CDs and drugs, as well as monitoring drugs with high sensitivity. Copyright © 2013 John Wiley & Sons, Ltd.

Flow-injection chemiluminescence analysis for sensitive determination of atenolol using cadmium sulfide quantum dots.

PubMed

Khataee, Alireza; Lotfi, Roya; Hasanzadeh, Aliyeh; Iranifam, Mortaza; Joo, Sang Woo

2016-03-15

A sensitive, rapid and simple flow-injection chemiluminescence (CL) system based on the light emitted from KMnO4-cadmium sulfide quantum dots (CdS QDs) reaction in the presence of cetyltrimethylammonium bromide (CTAB) in acidic medium was developed as a CL probe for the sensitive determination of atenolol. Optical and structural features of CdS QDs capped with l-cysteine, which synthesized via hydrothermal approach, were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence (PL), and UV-Vis spectroscopy. The CL intensity of KMnO4-CdS QDs-CTAB was remarkably enhanced in the presence of trace level of atenolol. Under optimum experimental conditions, there is a linear relationship between the increase in CL intensity of KMnO4-CdS QDs-CTAB system and atenolol concentration in a range of 0.001 to 4.0 mg L(-1) and 4.0 to 18.0 mg L(-1), with a detection limit (3σ) of 0.0010 mg L(-1). A possible mechanism for KMnO4-CdS QDs-CTAB-atenolol CL reaction is proposed. To prove the practical application of the KMnO4-CdS QDs-CTAB CL method, the method was applied for the determination of atenolol in spiked environmental water samples and commercial pharmaceutical formulation. Furthermore, corona discharge ionization ion mobility spectrometry (CD-IMS) technique was utilized for determination of atenolol. Copyright © 2015 Elsevier B.V. All rights reserved.

[Effects of different salt and alkali stresses on ion distribution in Red globe/Beta grapevines].

PubMed

Du, Yuan-peng; Jin, Xue-juan; Guo, Shu-hua; Fu, Qing-qing; Zhai, Heng

2015-06-01

The potted Red globe/Beta grapevines were selected to irrigated with NaCl, Na2SO4, NaHCO3, NH4Cl, (NH4)2SO4. Hence, the ions which induced leaf etiolation were screened and the impacts of different salt and alkali on ion distribution in different organs of grapevines were investigated. It was found that NaHCO3 exerted the greatest effects on grapevines, leaf etiolation at 14 days after treatment. By contrast, NaCl and NH4Cl treatments induced leaf etiolation at 28 days after treatment. The Na+ content in all the detected organs were significantly increased under NaHCO3 and NaCl treatment, and Na+ content in root under NaHCO3 treatment was 6.4 times as that in control root. NaHCO3 and NaCl treatments significantly decreased K+ content in the organs with the exception of leaf. NaHCO3 treatment significantly decreased K/Na in different organs, which declined to 0.1 in root. By contrast, NaCl treatment significantly decreased K/Na in the detected organs with exception of stem. Besides, the transport of Ca2+, Mg2+, Fe2+ to aboveground organs was significantly decreased by NaHCO3 and NaCl treatments. K/Na ratio in the detected organs were decreased under NH4Cl, (NH4) 2SO4 and Na2SO4 treatments, especially under NH4 Cl treatment. Taken together, NaHCO3 was the primary factor resulting in leaf etiolation, followed by NaCl and NH4Cl, while (NH4) 2SO4 and Na2SO4 produced impacts.

Laser-induced Fluorescence Spectroscopy for applications in chemical sensing and optical refrigeration

NASA Astrophysics Data System (ADS)

Kumi Barimah, Eric

Laser-induced breakdown spectroscopy (LIBS) is an innovative technique that has been used as a method for fast elemental analysis in real time. Conventional ultraviolet-visible (UV-VIS) LIBS has been applied to detect the elemental composition of different materials, including explosives, pharmaceutical drugs, and biological samples. The extension of conventional LIBS to the infrared region (˜1-12 mum) promises to provide additional information on molecular emission signatures due to rotational-vibrational transitions. In this research, a pulsed Nd: YAG laser operating at 1064 nm was focused onto several sodium compounds (NaCl, NaClO3, Na2CO3 and NaClO4) and potassium compounds (KCl, KClO3, K2CO3 and KClO4) to produce an intense plasma at the target surface. Several distinct infrared (IR) atomic emission signatures were observed from all sodium and potassium containing compounds. The atomic emission lines observed from the investigated samples matched assigned transitions of neutral sodium and potassium atoms published in the National Institute of Standards and Technology (NIST) atomic database. In addition to the intense atomic lines, the rst evidence of molecular LIBS emission structures were observed at ˜10.0 m in KClO3 and NaClO3 for the chlorate anion (ClO3 --1), at ˜6.7 to 8.0 mum in KNO3 and NaNO 3 for the nitrate anion (NO3--1 ), ˜8.0 to 10.0 mum in KClO4 and NaClO4 for perchlorate anion (ClO4--1 ), and ˜6.88 mum and 11.53 mum in Na2CO3 for the carbonate anion (CO3--1 ). The observed molecular emission showed strong correlation with the conventional Fourier Transform Infrared Spectrometry (FTIR) absorption spectra of the investigated samples. IR LIBS was also applied to determine the limit of detection (LOD) for the perchlorate anion in KClO4 using the 8.0 -11.0 mum IR-LIBS emission band. The calibration curve of ClO4 in KClO4 was constructed using peak and integrated emission intensities for known concentrations of mixed KClO4/NH4NO3 samples. The limit of detection for ClO4, was determined to be 14.7 +/- 0.5 wt%/wt for the given experimental conditions. In the second part of this research, the temperature-dependent absorption and emission properties of Tm doped KPb2Cl5 (KPC) and KPb2Br5 (KPB) were evaluated for applications in laser cooling. A Tm doped Y3Al5O12 (YAG) crystal was also included for comparative studies. Under laser pumping, all crystals exhibited broad IR fluorescence at room temperature with a mean fluorescence wavelength of ˜1.82 mum and bandwidth of 0.14 mum (FWHM) for Tm:KPC/KPB and ˜1.79 mum for Tm:YAG. Initial experiments on laser-induced heating/cooling were performed using a combined IR imaging and fluorescence thermometry setup. Employing a continuous-wave laser operating at 1.907 mum, Tm: KPC and Tm: KPB crystals revealed a very small heat load resulting in temperature increase of ˜ 0.3 ( +/- 0.1)°C. The heat loading in Tm:YAG was signicantly larger and resulted in a temperature increase of ˜0.9 (+/-0.1)°C. The results derived from IR imaging were also conrmed by the fluorescence thermometry experiments, which showed only minimal changes in the FIR intensity ratio of the green Er3+ fluorescence lines from Er:KPC.

Defined tetra-allelic gene disruption of the 4-coumarate:coenzyme A ligase 1 (Pv4CL1) gene by CRISPR/Cas9 in switchgrass results in lignin reduction and improved sugar release.

PubMed

Park, Jong-Jin; Yoo, Chang Geun; Flanagan, Amy; Pu, Yunqiao; Debnath, Smriti; Ge, Yaxin; Ragauskas, Arthur J; Wang, Zeng-Yu

2017-01-01

The development of genome editing technologies offers new prospects in improving bioenergy crops like switchgrass ( Panicum virgatum ). Switchgrass is an outcrossing species with an allotetraploid genome (2 n  = 4 x  = 36), a complexity which forms an impediment to generating homozygous knock-out plants. Lignin, a major component of the plant cell wall and a contributor to cellulosic feedstock's recalcitrance to decomposition, stands as a barrier to efficient biofuel production by limiting enzyme access to cell wall polymers during the fermentation process. We developed a CRISPR/Cas9 genome editing system in switchgrass to target a key enzyme involved in the early steps of monolignol biosynthesis, 4-Coumarate:coenzyme A ligase (4CL). Three 4CL genes, Pv4CL1 , Pv4CL2, and Pv4CL3 , were identified in switchgrass. Expression analysis revealed that Pv4CL1 transcripts were more abundant in the stem than in the leaf, while Pv4CL2 transcripts were barely detectable and Pv4CL3 was mainly expressed in the leaf. Pv4CL1 was selected as the target for CRISPR/Cas9 editing because of its preferential expression in highly lignified stem tissues. Specific guide RNA was constructed to target Pv4CL1 . After introducing the construct into switchgrass calli, 39 transgenic plants were regenerated. Using two rounds of PCR screening and sequencing, four plants were confirmed to have tetra-allelic mutations simultaneously. The Pv4CL1 knock-out plants had reduced cell wall thickness, an 8-30% reduction in total lignin content, a 7-11% increase in glucose release, and a 23-32% increase in xylose release. This study established a successful CRISPR/Cas9 system in switchgrass with mutation efficiency reaching 10%. The system allows the precise targeting of the selected Pv4CL1 gene to create switchgrass knock-out mutant plants with decreased lignin content and reduced recalcitrance.

The role of Te(IV) and Bi(III) chloride complexes in hydrothermal mass transfer: An X-ray absorption spectroscopic study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Etschmann, Barbara E.; Liu, Weihua; Pring, Allan

2016-05-01

Tellurium (Te) and bismuth (Bi) are two metal(loid)s often enriched together with gold (Au) in hydrothermal deposits; however the speciation and transport properties for these two metals in hydrothermal systems are poorly understood. We investigated the effect of chloride on the speciation of Te(IV) and Bi(III) in hydrothermal solutions using in-situ XAS spectroscopy. At ambient temperature, oxy-hydroxide complexes containing the [TeO3] moiety (e.g., H3TeO3+ under highly acidic conditions) predominate in salty solutions over a wide range in pH and salt concentrations. Te(IV)-Cl complexes only appear at pH(25 degrees C) <= 2 and high Cl- activity (>= 10). The highest ordermore » Te(IV) chloride complex detected is TeCl4(aq), and contains the [TeCl4] moiety. Upon heating to 199 degrees C, the Te(IV)-Cl complexes become more stable; however they still required highly acidic conditions which are likely to exist only in very limited environments in nature. At ambient temperature, Bi(III) is coordinated to 5.5(5) Cl atoms in high salinity, acidic (HCl >= 0.5 m) chloride solutions. This, combined with large EXAFS-derived structural disorder parameters, suggests that the Bi(III) complex is most likely present as both BiCl52- and BiCl63-. The number of Cl atoms coordinated to Bi(III) decreases with increasing temperature; at around 200 degrees C and above, Bi(III) is coordinated to three Cl atoms. Overall the data show that Te(IV) chloride complexes can be ignored in predicting Te mobility under oxidizing conditions in most geological environments, but that Bi(III) chloride complexes are expected to account for Bi mobility in acidic brines. New thermodynamic properties for Bi(III) chloride complexes are provided to improve reactive transport modeling of Bi up to 500 degrees C. Although higher order complexes such as BiCl52- and BiCl63- exist at ambient temperature, the BiCl3(aq) complex becomes the predominant chloride complex in saline solutions at T >= 200 degrees C.« less

Cl2O photochemistry: ultraviolet/vis absorption spectrum temperature dependence and O(3P) quantum yield at 193 and 248 nm.

PubMed

Papanastasiou, Dimitrios K; Feierabend, Karl J; Burkholder, James B

2011-05-28

The photochemistry of Cl(2)O (dichlorine monoxide) was studied using measurements of its UV/vis absorption spectrum temperature dependence and the O((3)P) atom quantum yield, Φ(Cl(2)O)(O)(λ), in its photolysis at 193 and 248 nm. The Cl(2)O UV/vis absorption spectrum was measured over the temperature range 201-296 K between 200 and 500 nm using diode array spectroscopy. Cl(2)O absorption cross sections, σ(Cl(2)O)(λ,T), at temperatures <296 K were determined relative to its well established room temperature values. A wavelength and temperature dependent parameterization of the Cl(2)O spectrum using the sum of six Gaussian functions, which empirically represent transitions from the ground (1)A(1) electronic state to excited states, is presented. The Gaussian functions are found to correlate well with published theoretically calculated vertical excitation energies. O((3)P) quantum yields in the photolysis of Cl(2)O at 193 and 248 nm were measured using pulsed laser photolysis combined with atomic resonance fluorescence detection of O((3)P) atoms. O((3)P) quantum yields were measured to be 0.85 ± 0.15 for 193 nm photolysis at 296 K and 0.20 ± 0.03 at 248 nm, which was also found to be independent of temperature (220-352 K) and pressure (17 and 28 Torr, N(2)). The quoted uncertainties are at the 2σ (95% confidence) level and include estimated systematic errors. ClO radical temporal profiles obtained following the photolysis of Cl(2)O at 248 nm, as reported previously in Feierabend et al. [J. Phys. Chem. A 114, 12052, (2010)], were interpreted to establish a <5% upper-limit for the O + Cl(2) photodissociation channel, which indicates that O((3)P) is primarily formed in the three-body, O + 2Cl, photodissociation channel at 248 nm. The analysis also indirectly provided a Cl atom quantum yield of 1.2 ± 0.1 at 248 nm. The results from this work are compared with previous studies where possible. © 2011 American Institute of Physics

Chromium mapping in male mice reproductive glands exposed to CrCl 3 using proton and X-ray synchrotron radiation microbeams

NASA Astrophysics Data System (ADS)

Ortega, R.; Devès, G.; Bonnin-Mosbah, M.; Salomé, M.; Susini, J.; Anderson, L. M.; Kasprzak, K. S.

2001-07-01

Preconception exposure to certain chemicals may increase risk of tumors in offspring, especially with regard to occupational metals such as chromium. However, the mechanism of chromium trans-generation carcinogenicity remains unknown. Using scanning proton X-ray microanalysis we have been able to detect chromium in testicular tissue sections from mice treated by intraperitoneal injection of 1 mmol/kg CrCl 3. Chromium concentration was about 5 μg/g dry mass in average, but higher concentrations were found within the limiting membrane of the testes, the tunica albuginea. In addition, synchrotron radiation X-ray fluorescence measurements, with microscopic resolution, clearly demonstrated the presence of chromium in the tunica albuginea but also within isolated cells from the interstitial connective tissue.

Enhancing and inhibiting effects of aromatic compounds on luminol-dimethylsulfoxide-OH(-) chemiluminescence and determination of intermediates in oxidative hair dyes by HPLC with chemiluminescence detection.

PubMed

Zhou, Jian; Xu, Hong; Wan, Guo-Hui; Duan, Chun-Feng; Cui, Hua

2004-10-08

The effect of 36 aromatic compounds on the luminol-dimethylsulfoxide-OH(-) chemiluminescence (CL) was systematically studied. It was found that dihydroxybenzenes, and ortho- and para-substituted aminophenols and phenylenediamines inhibited the CL and phenols with three or more than three hydroxyls except phloroglucin tended to enhance the CL. The CL inhibition and enhancement was proposed to be dependent on whether superoxide anion radical (O(2)(-)) was competitively consumed by compounds in the CL system. Trihydroxybenzenes were capable of generating superoxide anion radical, leading to the CL enhancement, whereas dihydroxybenzenes were superoxide anion radical scavenger, causing the CL inhibition. Based on the inhibited CL, a novel method for the simultaneous determination of p-phenylenediamine, o-phenylenediamine, p-aminophenol, o-aminophenol, resorcinol and hydroquinone by high-performance liquid chromatography coupled with chemiluminescence detection was developed. The method has been successfully applied to determine intermediates in oxidative hair dyes and wastewater of shampooing after hair dyed.

An Ru(II)-Fe(III) bimetallic complex as a multifunctional device for detecting, signal amplifying, and degrading oxalate.

PubMed

Chow, Cheuk-Fai; Ho, Pui-Yu; Gong, Cheng-Bin

2014-09-07

A tetranuclear bimetallic complex, [Ru(II)((t)Bubpy)(CN)4]2-[Fe(III)(H2O)3Cl]2·8H2O (1) has been synthesized and characterized. It was found to be a multifunctional device that can detect, signal amplify, and degrade an organic pollutant, oxalate. Results of the chemosensing studies of 1 toward common anions show that only oxalate selectively induces naked-eye colorimetric and luminometric responses with method detection limits down to 78.7 and 5.5 ppm, respectively from 1. Meanwhile, results of the photo-degradation studies of 1 toward oxalate show that the dissolved organic carbon content of oxalate decreased and reached complete mineralization into CO2 within 6 hours. Complex 1 was also found as the catalyst that amplified the detection signal toward oxalate. Through the photoassisted Fenton reaction by 1, methyl orange, an additional coloring agent, could be degraded so that the visual detection limit of 1 toward oxalate was magnified 50 times from 100 to 2 ppm. The detection, degradation, mineralization and signal amplification were found applicable in real water bodies such as river, pond and underground water with excellent recoveries and relative standard deviation.

Simulations of cm-wavelength Sunyaev-Zel'dovich galaxy cluster and point source blind sky surveys and predictions for the RT32/OCRA-f and the Hevelius 100-m radio telescope

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lew, Bartosz; Kus, Andrzej; Birkinshaw, Mark

We investigate the effectiveness of blind surveys for radio sources and galaxy cluster thermal Sunyaev-Zel'dovich effects (TSZEs) using the four-pair, beam-switched OCRA-f radiometer on the 32-m radio telescope in Poland. The predictions are based on mock maps that include the cosmic microwave background, TSZEs from hydrodynamical simulations of large scale structure formation, and unresolved radio sources. We validate the mock maps against observational data, and examine the limitations imposed by simplified physics. We estimate the effects of source clustering towards galaxy clusters from NVSS source counts around Planck-selected cluster candidates, and include appropriate correlations in our mock maps. The studymore » allows us to quantify the effects of halo line-of-sight alignments, source confusion, and telescope angular resolution on the detections of TSZEs. We perform a similar analysis for the planned 100-m Hevelius radio telescope (RTH) equipped with a 49-beam radio camera and operating at frequencies up to 22 GHz.We find that RT32/OCRA-f will be suitable for small-field blind radio source surveys, and will detect 33{sup +17}{sub −11} new radio sources brighter than 0.87 mJy at 30 GHz in a 1 deg{sup 2} field at > 5σ CL during a one-year, non-continuous, observing campaign, taking account of Polish weather conditions. It is unlikely that any galaxy cluster will be detected at 3σ CL in such a survey. A 60-deg{sup 2} survey, with field coverage of 2{sup 2} beams per pixel, at 15 GHz with the RTH, would find <1.5 galaxy clusters per year brighter than 60 μJy (at 3σ CL), and would detect about 3.4 × 10{sup 4} point sources brighter than 1 mJy at 5σ CL, with confusion causing flux density errors ∼< 2% (20%) in 68% (95%) of the detected sources.A primary goal of the planned RTH will be a wide-area (π sr) radio source survey at 15 GHz. This survey will detect nearly 3 × 10{sup 5} radio sources at 5σ CL down to 1.3 mJy, and tens of galaxy clusters, in one year of operation with typical weather conditions. Confusion will affect the measured flux densities by ∼< 1.5% (16%) for 68% (95%) of the point sources. We also gauge the impact of the RTH by investigating its performance if equipped with the existing RT32 receivers, and the performance of the RT32 equipped with the RTH radio camera.« less

NaCl intake and preference threshold of spontaneously hypertensive rats.

PubMed

Fregly, M J

1975-09-01

Both male and female spontaneously hypertensive (SH) rats have an appetite for NaCl solution. The appetite is present when a choice is offered between distilled water and either isotonic or hypertonic (0.25 M) NaCl solution to drink. Total fluid intake (water plus NaCl solution) was greater for SH rats than for controls while food intakes (g/100 g body wt/day) of SH rats were not different from controls. Mean body weight of SH rats was always less than that of controls. The appetite for NaCl solution was accompanied by a significant reduction in preference (detection) threshold. SH rats could detect the difference between distilled water and NaCl solution when the concentration of the latter was 12 mEq/liter compared to a control threshold of 30 mEq/liter. The NaCl appetite and reduced NaCl preference threshold induced by spontaneous hypertension is in marked contrast to the NaCl aversion induced by other types of experimentally induced hypertension in rats. The mechanism or mechanisms responsible for these differences remain for further study.

Excimer-monomer switch: a reaction-based approach for selective detection of fluoride.

PubMed

Song, Qiao; Bamesberger, Angela; Yang, Lingyun; Houtwed, Haley; Cao, Haishi

2014-07-21

A N-aryl-1,8-naphthalimide based sensor (ES-1) bearing a trimethylsilyl ether has been synthesized by a two-step reaction for quantitative detection of fluoride (F(-)). ES-1 exhibited monomer/excimer emissions at 410 and 524 nm respectively in CH2Cl2. In the presence of F(-), the desilylation of trimethylsilyl ether caused decay of the excimer emission as well as enhancement of the monomer emission to give a ratiometric signal. The fluoride-triggered desilylation showed a high reaction rate and high affinity to F(-) over nine other interfering anions. ES-1 provided a novel fluorescence assay based on excimer-monomer switch of N-aryl-1,8-naphthalimide to quantitatively measure F(-) with a detection limit of 0.133 ppm.

Visual colorimetry for trace antimony(V) by ion-pair solid-phase extraction with bis[2-(5-chloro-2-pyridylazo)-5-diethylaminophenolato]cobalt(III) on a PTFE type membrane filter.

PubMed

Mizuguchi, Hitoshi; Matsuda, Yuki; Mori, Takehito; Uehara, Atsushi; Ishikawa, Yuta; Endo, Masatoshi; Shida, Junichi

2008-02-01

A new visual colorimetry for trace antimony(V) based on ion-pair solid-phase extraction to a PTFE-type membrane filter with bis[2-(5-chloro-2-pyridylazo)-5-diethylaminophenolato]cobalt(III) ion ([Co(5-Cl-PADAP)(2)](+)) has been developed. Experiments showed that hexachloroantimonate(V) ion (SbCl(6)(-)) was adsorbed with [Co(5-Cl-PADAP)(2)](+) to the front surface of the PTFE filter. The adsorption of antimony(V) ion was promoted by the addition of lithium chloride as a source of chloride ion. The excess reagent of [Co(5-Cl-PADAP)(2)](+) was eluted by rinsing with a 10 wt% methanol aqueous solution. In this case, the slow rate of the hydrolysis reaction of SbCl(6)(-) and the difference of the hydrophobicity of the ion pairs were important for adsorption and separation with a PTFE-type membrane filter. The antimony(V) concentration was determined through a visual comparison with a standard series. The visual detection limit was 0.10 microg. The calibration curve assessed with the reflection spectrometric responses at 580 nm was linear in the concentration range of 0.10 - 1.2 microg (r = 0.996). The proposed method has been applied to the determination of sub-microgram levels of antimony(V) ion in water samples.

An Environmental Friendly Procedure for Photometric Determination of Hypochlorite in Tap Water Employing a Miniaturized Multicommuted Flow Analysis Setup

PubMed Central

Borges, Sivanildo S.; Reis, Boaventura F.

2011-01-01

A photometric procedure for the determination of ClO− in tap water employing a miniaturized multicommuted flow analysis setup and an LED-based photometer is described. The analytical procedure was implemented using leucocrystal violet (LCV; 4,4′,4′′-methylidynetris (N,N-dimethylaniline), C25H31N3) as a chromogenic reagent. Solenoid micropumps employed for solutions propelling were assembled together with the photometer in order to compose a compact unit of small dimensions. After control variables optimization, the system was applied for the determination of ClO− in samples of tap water, and aiming accuracy assessment samples were also analyzed using an independent method. Applying the paired t-test between results obtained using both methods, no significant difference at the 95% confidence level was observed. Other useful features include low reagent consumption, 2.4 μg of LCV per determination, a linear response ranging from 0.02 up to 2.0 mg L−1  ClO−, a relative standard deviation of 1.0% (n = 11) for samples containing 0.2 mg L−1  ClO−, a detection limit of 6.0 μg L−1  ClO−, a sampling throughput of 84 determinations per hour, and a waste generation of 432 μL per determination. PMID:21747732

Flow injection chemiluminescence determination of loxoprofen and naproxen with the acidic permanganate-sulfite system

PubMed Central

Wang, Li-Juan; Tang, Yu-Hai; Liu, Yang-Hao

2012-01-01

A novel flow injection chemiluminescence (CL) method for the determination of loxoprofen and naproxen was proposed based on the CL system of KMnO4, and Na2SO3 in acid media. The CL intensity of KMnO4-Na2SO3 was greatly enhaneed in the presence of loxoprofen and naproxen. The mechanism of the CL reaction was studied by the kinetic proecss and UV-vis absorption and the conditions were optimized. Under optimized conditions, the CL intensity was linear with loxoprofen and naproxen concentration in the range of 7.0 × 10−8 – 1.0 × 10−5 g/mL and 2.0 × 10−7 – 4.0 × 10−6 g/mL with the detection limit of 2.0 × 10−8 g/mL and 3.0 × 10−8 g/mL (S/N = 3), respectively. Thc relative standard deviations were 2.39% and 1.37% for 5.0 × 10−7 g/mL naproxen and 5.0 × 10−7 g/mL loxoprofen (n = 10), respectively. The proposed method was satisfactorily applied to thc determination of loxoprofen and naproxen in pharmaceutical preparations. PMID:29403682

Enhancement of periodate-hydrogen peroxide chemiluminescence by nitrogen doped carbon dots and its application for the determination of pyrogallol and gallic acid.

PubMed

Shah, Syed Niaz Ali; Li, Haifang; Lin, Jin-Ming

2016-06-01

A new sensitized chemiluminescence (CL) was developed to broaden the analytical application of KIO4-H2O2 system. The nitrogen doped carbon dots (N-CDs) dramatically boosted the CL intensity of KIO4-H2O2 system which was further enriched by basic medium. In light of EPR analysis, free radical scavenging studies and CL spectra the detail mechanism for the enhancement was conferred in the presence of N-CDs and NaOH. The results suggested that CL of KIO4-H2O2 system in the presence and absence of N-CDs and NaOH proceeds via radical pathway. The enhanced CL was used for the determination of pyrogallol and gallic acid in range of 1.0×10(-4)-1.0×10(-7)M with 4.6×10(-8) and 6.1×10(-8)M limit of detection respectively. The relative standard deviation (RSD) at a concentration of 10(-5) for gallic acid and pyrogallol was 1.4% and 2.3% respectively (n=11). The attained results unveil that the present method is sensitive, faster, simpler and less costly compared to other methods and could be applied to determine polyphenols in real samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Method for Derivatization and Detection of Chemical Weapons Convention Related Sulfur Chlorides via Electrophilic Addition with 3-Hexyne.

PubMed

Goud, D Raghavender; Pardasani, Deepak; Purohit, Ajay Kumar; Tak, Vijay; Dubey, Devendra Kumar

2015-07-07

Sulfur monochloride (S2Cl2) and sulfur dichloride (SCl2) are important precursors of the extremely toxic chemical warfare agent sulfur mustard and classified, respectively, into schedule 3.B.12 and 3.B.13 of the Chemical Weapons Convention (CWC). Hence, their detection and identification is of vital importance for verification of CWC. These chemicals are difficult to detect directly using chromatographic techniques as they decompose and do not elute. Until now, the use of gas chromatographic approaches to follow the derivatized sulfur chlorides is not reported in the literature. The electrophilic addition reaction of sulfur monochloride and sulfur dichloride toward 3-hexyne was explored for the development of a novel derivatization protocol, and the products were subjected to gas chromatography-mass spectrometric (GC-MS) analysis. Among various unsaturated reagents like alkenes and alkynes, symmetrical alkyne 3-hexyne was optimized to be the suitable derivatizing agent for these analytes. Acetonitrile was found to be the suitable solvent for the derivatization reaction. The sample preparation protocol for the identification of these analytes from hexane spiked with petrol matrix was also optimized. Liquid-liquid extraction followed by derivatization was employed for the identification of these analytes from petrol matrix. Under the established conditions, the detection and quantification limits are 2.6 μg/mL, 8.6 μg/mL for S2Cl2 and 2.3 μg/mL, 7.7 μg/mL for SCl2, respectively, in selected ion monitoring (SIM) mode. The calibration curve had a linear relationship with y = 0.022x - 0.331 and r(2) = 0.992 for the working range of 10 to 500 μg/mL for S2Cl2 and y = 0.007x - 0.064 and r(2) = 0.991 for the working range of 10 to 100 μg/mL for SCl2, respectively. The intraday RSDs were between 4.80 to 6.41%, 2.73 to 6.44% and interday RSDs were between 2.20 to 7.25% and 2.34 to 5.95% for S2Cl2 and SCl2, respectively.

An aptamer-based immunoassay in microchannels of a portable analyzer for detection of microcystin-leucine-arginine.

PubMed

Xiang, An; Lei, Xiaoying; Ren, Fengling; Zang, Liuqin; Wang, Qin; Zhang, Ju; Lu, Zifan; Guo, Yanhai

2014-12-01

The rapid detection of microcystin-leucine-arginine (MC-LR), the most highly toxic among MCs, is significantly important to environmental and human health protection and prevention of MC-LR from being used as a bioweapon. Although aptamers offer higher affinity, specificity, and stability with MC-LR than antibodies in the immunodetection of MC-LR due to steric hindrance between two antibodies and limited epitopes of MC-LR for use in a sandwich immunoassay, no sandwich immunoassay using an aptmer has been developed for MC-LR detection. This study is aimed at developing an aptamer-antibody immunoassay (AAIA) to detect MC-LR using a portable analyzer. The aptamers were immobilized onto the glass surface of a microchamber to capture MC-LR. MC-LR and horseradish peroxidase (HRP)-labeled antibody were pulled into the microchamber to react with the immobilized aptamer. The chemiluminescence (CL) catalyzed by HRP was tested by a photodiode-based portable analyzer. MC-LR at 0.5-4.0 μg/L was detected quantitatively by the AAIA, with a CL signal sensitivity of 0.3 μg/L. The assay took less than 35 min for a single sample and demonstrated a high specificity, detecting only MC-LR, but not MC-LA, MC-YR, or nodularin-R. The recovery of two spiked real environmental samples calculated as 94.5-112.7%. Therefore, this AAIA was proved to be a rapid and simple method to detect MC-LR in the field by a single analyst. Copyright © 2014 Elsevier B.V. All rights reserved.

Novel miniaturized sensors for potentiometric batch and flow-injection analysis (FIA) of perchlorate in fireworks and propellants.

PubMed

Almeer, Saeed H M A; Zogby, Ibrahim A; Hassan, Saad S M

2014-11-01

Three planar miniaturized perchlorate membrane sensors (3×5 mm(2)) are prepared using a flexible Kaptan substrate coated with nitron-perchlorate (NT-ClO4) [sensor 1], methylene blue-perchlorate (MB-ClO4) [sensor II] and indium-porphyrin (In-Por) [sensor III] as electroactive materials in PVC membranes plasticized with 2-NPPE. Sensors I, II and III display near-Nernstian response for 1.0×10(-5)-1.0×10(-2), 3.1×10(-5)-1.0×10(-2) and 3.1×10(-6)-1.0×10(-2) mol L(-1) ClO4(-) with lower detection limits of 6.1×10(-6), 6.9×10(-6) and 1.2×10(-6) mol L(-1), and anionic calibration slopes of 50.9±0.4, 48.4±0.4 and 57.7±0.3 mV decade(-1), respectively. Methods for determining perchlorate using these sensors offer many attractive advantages including simplicity, flexibility, cost effectiveness, wide linear dynamic response range (0.1-1000 ppm), low detection limit (<1.2×10(-6) mol L(-1)≡0.1 ppm), small sample test volume (100 μL), safety, short response time (<20 s), long life span (~8 weeks), and extended wide working pH range (4.5-8.0). The sensors show high selectivity in the presence of some inorganic ions (e.g., PO4(3-), SO4(2-), S2O3(2-), NO2(-), NO3(-), N3(-), CN(-), Cl(-), Br(-), I(-)) and automation feasibility. Indium-porphyrin based membrane sensor (sensor III) is used as a detector in a wall-jet flow injection set-up to enable accurate flow injection analysis (FIA) of perchlorate in some fireworks without interferences from the associated reducing agents (sulfur and charcoal), binders (dextrin, lactose), coloring agents (calcium, strontium, copper, iron, sodium), color brighten (linseed oil) and regulators (aluminum flakes) which are commonly used in the formulations. The sensor is also used for perchlorate assessment in some propellant powders. The results fairly agree with data obtained by ion-chromatography. Copyright © 2014 Elsevier B.V. All rights reserved.

Search for Primordial Black Holes with the Whipple Atmospheric Cerenkov Telescope

NASA Astrophysics Data System (ADS)

Linton, Eric

2005-04-01

Stephen Hawking's prediction that black holes should radiate like black bodies has several important consequences, including the possibility for the detection of small (˜10^15 g) black holes created in the very early universe. The detection of such primordial black holes (PBHs) would not only validate Hawking's theory, but would provide useful insights into the history of the early universe. A search through 5.5 years of archival data from the Whipple Atmospheric Cerenkov Telescope was made for TeV gamma-ray bursts on 1 s, 3 s, and 5 s timescales. Based on a null result, an upper-limit on the evaporation rate of PBHs of 2.69 x10^6 pc-3 yr^- 1 (99% CL) was made, assuming the Standard Model of particle physics. When combined with the results of an earlier search through Whipple data, this limit was lowered to 1.33 x10^6 pc-3 yr-1, which is nearly a factor of 2 better than the previous limit at this energy range.

Disk stars in the Milky Way detected beyond 25 kpc from its center

NASA Astrophysics Data System (ADS)

López-Corredoira, M.; Allende Prieto, C.; Garzón, F.; Wang, H.; Liu, C.; Deng, L.

2018-05-01

Context. The maximum size of the Galactic stellar disk is not yet known. Some studies have suggested an abrupt drop-off of the stellar density of the disk at Galactocentric distances R ≳ 15 kpc, which means that in practice no disk stars or only very few of them should be found beyond this limit. However, stars in the Milky Way plane are detected at larger distances. In addition to the halo component, star counts have placed the end of the disk beyond 20 kpc, although this has not been spectroscopically confirmed so far. Aims: Here, we aim to spectroscopically confirm the presence of the disk stars up to much larger distances. Methods: With data from the LAMOST and SDSS-APOGEE spectroscopic surveys, we statistically derived the maximum distance at which the metallicity distribution of stars in the Galactic plane is distinct from that of the halo populations. Results: Our analysis reveals the presence of disk stars at R > 26 kpc (99.7% C.L.) and even at R > 31 kpc (95.4% C.L.).

Bomb-Pulse Chlorine-36 at the Proposed Yucca Mountain Repository Horizon: An Investigation of Previous Conflicting Results and Collection of New Data

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cizdziel, James

2006-07-31

Previous studies Los Alamos National Laboratory (LANL) found elevated ratios of chlorine-36 to total chloride (36Cl/Cl) in samples of rock collected from the Exploratory Studies Facility (ESF) at Yucca Mountain (YM). The data were interpreted as an indication that fluids containing “bomb-pulse” 36Cl reached the repository horizon in the ~50 years since the peak period of above-ground nuclear testing. Due to the significance of 36Cl data to conceptual models of unsaturated zone flow, the United States Geological Survey (USGS) implemented a study to validate the LANL findings. The USGS drilled new boreholes at select locations across zones where bomb-pulse ratiosmore » had previously been identified. The drill cores were analyzed at Lawrence Livermore National Laboratory (LLNL). Because consensus was not reached between the USGS/LLNL and LANL on several fundamental points including the presence or absence of bomb-pulse 36Cl, an evaluation by the University of Nevada, Las Vegas (UNLV), was initiated. The overall objectives of the UNLV study were to investigate the source of the validation study’s conflicting results, and to obtain additional data on bomb-pulse isotopes at the repository horizon. UNLV engaged in discussions with previous investigators, reviewed reports, and analyzed archived samples. UNLV also collected new samples of rock from the ESF, soil profiles from the surface of YM, and samples of seep water from inside the ESF. Samples were analyzed for 36Cl/Cl ratios, and 99Tc and 129I in select samples. A column experiment was conducted mimicking the passage of bomb-pulse 36Cl through YM tuff. The work faced several obstacles including an extended shutdown of the tunnel. Only one sample yielded a background corrected 36Cl/Cl ratio that was higher than the accepted bomb-pulse threshold (1250 x 10-15). Specimen 01034214 obtained from the Drill Hole Wash fault (19+33) had a ratio of 1590 ± 80 (1σ) x10-15, whereas the other separate sample from this fault zone yielded 1160 ± 50 (1σ) x 10-15. Three samples collected from Alcove 6 averaged 490 ± 100 (1σ) x10-15; a sample from Sundance Fault resulted in a ratio of 920 ± 60 (1σ) x10-15, and a sample from the Bow Ridge Fault produced 530 ± 20 (1σ) x10-15. The results are significant because: 1) they tend to be lower than LANL data for comparable samples, albeit in agreement with the range of data produced in the area, and 2) they show that a bomb-pulse 36Cl/Cl ratio was measured in rock collected at the repository horizon level by a second and independent group of investigators (UNLV). Because of time UNLV was not able to replicate the results, and these few data points are insufficient to draw major and definitive conclusions. Leachates of soil samples collected from the surface above the ESF yielded several ratios with bomb-pulse 36Cl, particularly for samples encompassing the wetting front. Soil samples collected above the south ramp, where there was limited soil coverage due to a large amount of rock outcrop, had relatively large ratios ranging from 2170 ± 110 (1σ) x10-15 to 5670 ± 350 (1σ) x10-15. Soil samples from profiles from above the north ramp ranged from 820 ± 70 (1σ) x10-15 to 2390 ± 160 (1σ) x10-15, which compare favorably with previous measurements near the site. Water seepage into the ESF south ramp and 36Cl standards made from NIST material were also analyzed. The standards were produced to have nominal 36Cl/Cl ratios (10-15) of 500, 2,500 and 10,000 and the results showed good agreement with the calculated ratios. The seepage samples ranged between 680 ± 40 (1σ) x10-15 to 1110 ± 40 (1σ) x10-15, consistent with that found for modern meteoric water, with a small bomb-pulse component. Bomb-pulse 36Cl may not have been incorporated in this fast-path water because the surface above the infiltration zone consists mostly of outcrop and the flow pathways have probably mostly been leached. 99Tc was measured in five of nine leaches of ESF rock but poor analytical recoveries and lack of data overlap with 36Cl limit interpretations of these data. The detection capability of the ICP-MS was insufficient for measuring 129I without preconcentration, and detection by AMS may be preferable. Experiments were conducted using bromide instead of chloride as a carrier, which is advantageous because it may eliminate the need for blank subtraction. ESF samples prepared using bromide had 36Cl/Cl ratios (x10-15) with acceptable levels of uncertainty (1σ): 720 ± 30 and 1250 ± 90 for Bow Ridge and Drill Hole Wash Faults, respectively. The result for the latter is noteworthy because it constitutes a second detection of a 36Cl/Cl bomb-pulse ratio at the site, albeit from a non-Q measurement. The source of the conflicting results between USGS/LLNL and LANL could not be determined. There was no evidence that the different AMS facilities were a source of the discrepancy between the results.« less

Recommendations for processing atmospheric attenuated backscatter profiles from Vaisala CL31 ceilometers

NASA Astrophysics Data System (ADS)

Kotthaus, Simone; O'Connor, Ewan; Münkel, Christoph; Charlton-Perez, Cristina; Haeffelin, Martial; Gabey, Andrew M.; Grimmond, C. Sue B.

2016-08-01

Ceilometer lidars are used for cloud base height detection, to probe aerosol layers in the atmosphere (e.g. detection of elevated layers of Saharan dust or volcanic ash), and to examine boundary layer dynamics. Sensor optics and acquisition algorithms can strongly influence the observed attenuated backscatter profiles; therefore, physical interpretation of the profiles requires careful application of corrections. This study addresses the widely deployed Vaisala CL31 ceilometer. Attenuated backscatter profiles are studied to evaluate the impact of both the hardware generation and firmware version. In response to this work and discussion within the CL31/TOPROF user community (TOPROF, European COST Action aiming to harmonise ground-based remote sensing networks across Europe), Vaisala released new firmware (versions 1.72 and 2.03) for the CL31 sensors. These firmware versions are tested against previous versions, showing that several artificial features introduced by the data processing have been removed. Hence, it is recommended to use this recent firmware for analysing attenuated backscatter profiles. To allow for consistent processing of historic data, correction procedures have been developed that account for artefacts detected in data collected with older firmware. Furthermore, a procedure is proposed to determine and account for the instrument-related background signal from electronic and optical components. This is necessary for using attenuated backscatter observations from any CL31 ceilometer. Recommendations are made for the processing of attenuated backscatter observed with Vaisala CL31 sensors, including the estimation of noise which is not provided in the standard CL31 output. After taking these aspects into account, attenuated backscatter profiles from Vaisala CL31 ceilometers are considered capable of providing valuable information for a range of applications including atmospheric boundary layer studies, detection of elevated aerosol layers, and model verification.

Self-Catalyzing Chemiluminescence of Luminol-Diazonium Ion and Its Application for Catalyst-Free Hydrogen Peroxide Detection and Rat Arthritis Imaging.

PubMed

Zhao, Chunxin; Cui, Hongbo; Duan, Jing; Zhang, Shenghai; Lv, Jiagen

2018-02-06

We report the unique self-catalyzing chemiluminescence (CL) of luminol-diazonium ion (N 2 + -luminol) and its analytical potential. Visual CL emission was initially observed when N 2 + -luminol was subjected to alkaline aqueous H 2 O 2 without the aid of any catalysts. Further experimental investigations found peroxidase-like activity of N 2 + -luminol on the cleavage of H 2 O 2 into OH • radical. Together with other experimental evidence, the CL mechanism is suggested as the activation of N 2 + -luminol and its dediazotization product 3-hydroxyl luminol by OH • radical into corresponding intermediate radicals, and then further oxidation to excited-state 3-N 2 + -phthalic acid and 3-hydroxyphthalic acid, which finally produce 415 nm CL. The self-catalyzing CL of N 2 + -luminol provides us an opportunity to achieve the attractive catalyst-free CL detection of H 2 O 2 . Experiments demonstrated the 10 -8 M level detection sensitivity to H 2 O 2 as well as to glucose or uric acid if presubjected to glucose oxidase or uricase. With the exampled determination of serum glucose and uric acid, N 2 + -luminol shows its analytical potential for other analytes linking the production or consumption of H 2 O 2 . Under physiological condition, N 2 + -luminol exhibits highly selective and sensitive CL toward 1 O 2 among the common reactive oxygen species. This capacity supports the significant application of N 2 + -luminol for detecting 1 O 2 in live animals. By imaging the arthritis in LEW rats, N 2 + -luminol CL is demonstrated as a potential tool for mapping the inflammation-relevant biological events in a live body.

Corrosivities in a pilot-scale combustor of a British and two Illinois coals with varying chlorine contents

USGS Publications Warehouse

Chou, I.-Ming; Lytle, J.M.; Kung, S.C.; Ho, K.K.

2000-01-01

Many US boiler manufacturers have recommended limits on the chlorine (Cl) content (< 0.25% or < 0.3%) of coals to be used in their boilers. These limits were based primarily on extrapolation of British coal data to predict the probable corrosion behavior of US coals. Even though Cl-related boiler corrosion has not been reported by US utilities burning high-Cl Illinois coals, the manufacturer's limits affect the marketability of high-Cl Illinois coals. This study measured the relative rates of corrosion caused by two high-Cl coals (British and Illinois) and one low-Cl Illinois baseline coal under identical pilot-scale combustion conditions for about 1000 h which gave reliable comparisons. Temperatures used reflected conditions in boiler superheaters. The corrosion probes were fabricated from commercial alloy 304SS frequently used at the hottest superheater section of utility boilers. The results showed no evidence of direct correlation between the coal chlorine content and rate of corrosion. A correlation between the rate of corrosion and the metal temperature was obvious. The results suggested that the different field histories of corrosivity from burning high-Cl Illinois coal and high-Cl British coal occurred because of different metal temperatures operated in US and UK utility boilers. The results of this study can be combined into a database, which could be used for lifting the limits on chlorine contents of coals burned in utility boilers in the US.

Potential tracers for tracking septic tank effluent discharges in watercourses.

PubMed

Richards, Samia; Withers, Paul J A; Paterson, Eric; McRoberts, Colin W; Stutter, Marc

2017-09-01

Septic tank effluent (STE) contributes to catchment nutrient and pollutant loads. To assess the role of STE discharges in impairment of surface water, it is essential to identify the sources of pollution by tracing contaminants in watercourses. We examined tracers that were present in STE to establish their potential for identifying STE contamination in two stream systems (low and high dilution levels) against the background of upstream sources. The studied tracers were microbial, organic matter fluorescence, caffeine, artificial sweeteners and effluent chemical concentrations. The results revealed that tracer concentration ratios Cl/EC, Cl/NH 4 -N, Cl/TN, Cl/TSS, Cl/turbidity, Cl/total coliforms, Cl/sucralose, Cl/saccharin and Cl/Zn had potential as tracers in the stream with low dilution level (P < 0.05). Fluorescence spectroscopy could detect STE inputs through the presence of the tryptophan-like peak, but was limited to water courses with low level of dilution and was positively correlated with stream Escherichia coli (E. coli) and soluble reactive phosphorus (SRP). The results also suggested that caffeine and artificial sweeteners can be suitable tracers for effluent discharge in streams with low and high level of dilution. Caffeine and saccharin were positively correlated with faecal coliforms, E. coli, total P and SRP, indicating their potential to trace discharge of a faecal origin and to be a marker for effluent P. Caffeine and SRP had similar attenuation behaviour in the receiving stream waters suggesting caffeine's potential role as a surrogate indicator for the behaviour of P downstream of effluent inputs. Taken together, results suggest that a single tracer alone was not sufficient to evaluate STE contamination of watercourses, but rather a combination of multiple chemical and physical tracing approaches should be employed. A multiple tracing approach would help to identify individual and cumulative STE inputs that pose risks to stream waters in order to prioritise and target effective mitigation measures. Copyright © 2017 Elsevier Ltd. All rights reserved.

Point Source Polarimetry with the Gemini Planet Imager: Sensitivity Characterization with T5.5 Dwarf Companion HD 19467 B

NASA Technical Reports Server (NTRS)

Jensen-Clem, Rebecca; Millar-Blanchaer, Max; Mawet, Dimitri; Graham, James R.; Wallace, J. Kent; Macintosh, Bruce; Hinkley, Sasha; Wiktorowicz, Sloane J.; Perrin, Marshall D.; Marley, Mark S.;

Rapid and sensitive detection of Lily symptomless virus by reverse transcription loop-mediated isothermal amplification.

PubMed

He, Xiangfeng; Xue, Fei; Xu, Shufa; Wang, Wenhe

2016-12-01

Lily symptomless virus (LSV) is one of the most prevalent viruses that infect lily plants worldwide. A rapid and sensitive reverse transcription loop-mediated isothermal amplification (RT-LAMP) assay was developed for detection of LSV, using two primer pairs that specifically amplified the conserved sequence of LSV coat protein. The optimum reaction conditions were as follows: 4mM MgCl 2 and 0.8M betaine with incubation at 64°C for 30min. The limit of detection of LSV from infected lily leaves was 10-fold higher for RT-LAMP than for conventional RT-PCR. Moreover, RT-LAMP detected LSV in not only symptomatic, but also in symptomless tissues of infected plants. These findings indicate that our RT-LAMP method for LSV can serve as a low-cost, simple, and rapid alternative to conventional detection assays. Copyright © 2016 Elsevier B.V. All rights reserved.

Point source polarimetry with the Gemini planet imager: Sensitivity characterization with T5.5 dwarf companion HD 19467 B

DOE PAGES

Jensen-Clem, Rebecca; Millar-Blanchaer, Max; Mawet, Dimitri; ...

2016-03-29

Detecting polarized light from self-luminous exoplanets has the potential to provide key information about rotation, surface gravity, cloud grain size, and cloud coverage. While field brown dwarfs with detected polarized emission are common, no exoplanet or substellar companion has yet been detected in polarized light. With the advent of high contrast imaging spectro-polarimeters such as GPI and SPHERE, such a detection may now be possible with careful treatment of instrumental polarization. In this paper, we present 28 minutes of H-band GPI polarimetric observations of the benchmark T5.5 companion HD 19467 B. We detect no polarization signal from the target, and place an upper limit on the degree of linear polarization ofmore » $${p}_{\\mathrm{CL}99.73\\%}\\leqslant 2.4\\%$$. In conclusion, we discuss our results in the context of T dwarf cloud models and photometric variability.« less

System-on-fluidics immunoassay device integrating wireless radio-frequency-identification sensor chips.

PubMed

Yazawa, Yoshiaki; Oonishi, Tadashi; Watanabe, Kazuki; Shiratori, Akiko; Funaoka, Sohei; Fukushima, Masao

2014-09-01

A simple and sensitive point-of-care-test (POCT) device for chemiluminescence (CL) immunoassay was devised and tested. The device consists of a plastic flow-channel reactor and two wireless-communication sensor chips, namely, a photo-sensor chip and a temperature-sensor chip. In the flow-channel reactor, a target antigen is captured by an antibody immobilized on the inner wall of the flow-channel and detected with enzyme labeled antibody by using CL substrate. The CL signal corresponding to the amount of antigen is measured by a newly developed radio-frequency-identification (RFID) sensor, which enables batteryless operation and wireless data communication with an external reader. As for the POCT device, its usage environment, especially temperature, varies for each measurement. Hence, temperature compensation is a key issue in regard to eliminating dark-signal fluctuation, which is a major factor in deterioration of the precision of the POCT device. A two-stage temperature-compensation scheme was adopted. As for the first stage, the signals of two photodiodes, one with an open window and one with a sealed window, integrated on the photo-sensor chip are differentiated to delete the dark signal. As for the second stage, the differentiated signal fluctuation caused by a temperature variation is compensated by using the other sensor chip (equipped with a temperature sensor). The dark-level fluctuation caused by temperature was reduced from 0.24 to 0.02 pA/°C. The POCT device was evaluated as a CL immunoassay of thyroid-stimulating hormone (TSH). The flow rate of the CL reagent in the flow channel was optimized. As a result, the detection limit of the POCT device was 0.08 ng/ml (i.e., 0.4 μIU/ml). Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Scanning Electron Microscope-Cathodoluminescence Analysis of Rare-Earth Elements in Magnets.

PubMed

Imashuku, Susumu; Wagatsuma, Kazuaki; Kawai, Jun

2016-02-01

Scanning electron microscope-cathodoluminescence (SEM-CL) analysis was performed for neodymium-iron-boron (NdFeB) and samarium-cobalt (Sm-Co) magnets to analyze the rare-earth elements present in the magnets. We examined the advantages of SEM-CL analysis over conventional analytical methods such as SEM-energy-dispersive X-ray (EDX) spectroscopy and SEM-wavelength-dispersive X-ray (WDX) spectroscopy for elemental analysis of rare-earth elements in NdFeB magnets. Luminescence spectra of chloride compounds of elements in the magnets were measured by the SEM-CL method. Chloride compounds were obtained by the dropwise addition of hydrochloric acid on the magnets followed by drying in vacuum. Neodymium, praseodymium, terbium, and dysprosium were separately detected in the NdFeB magnets, and samarium was detected in the Sm-Co magnet by the SEM-CL method. In contrast, it was difficult to distinguish terbium and dysprosium in the NdFeB magnet with a dysprosium concentration of 1.05 wt% by conventional SEM-EDX analysis. Terbium with a concentration of 0.02 wt% in an NdFeB magnet was detected by SEM-CL analysis, but not by conventional SEM-WDX analysis. SEM-CL analysis is advantageous over conventional SEM-EDX and SEM-WDX analyses for detecting trace rare-earth elements in NdFeB magnets, particularly dysprosium and terbium.

Development of a PCR/LDR/flow-through hybridization assay using a capillary tube, probe DNA-immobilized magnetic beads and chemiluminescence detection.

PubMed

Hommatsu, Manami; Okahashi, Hisamitsu; Ohta, Keisuke; Tamai, Yusuke; Tsukagoshi, Kazuhiko; Hashimoto, Masahiko

2013-01-01

A polymerase chain reaction (PCR)/ligase detection reaction (LDR)/flow-through hybridization assay using chemiluminescence (CL) detection was developed for analyzing point mutations in gene fragments with high diagnostic value for colorectal cancers. A flow-through hybridization format using a capillary tube, in which probe DNA-immobilized magnetic beads were packed, provided accelerated hybridization kinetics of target DNA (i.e. LDR product) to the probe DNA. Simple fluid manipulations enabled both allele-specific hybridization and the removal of non-specifically bound DNA in the wash step. Furthermore, the use of CL detection greatly simplified the detection scheme, since CL does not require a light source for excitation of the fluorescent dye tags on the LDR products. Preliminary results demonstrated that this analytical system could detect both homozygous and heterozygous mutations, without the expensive instrumentation and cumbersome procedures required by conventional DNA microarray-based methods.

Chemiluminescence immunoassay for the rapid and sensitive detection of antibody against porcine parvovirus by using horseradish peroxidase/detection antibody-coated gold nanoparticles as nanoprobes.

PubMed

Zhou, Yuan; Zhou, Tao; Zhou, Rui; Hu, Yonggang

2014-06-01

A rapid, simple, facile, sensitive and enzyme-amplified chemiluminescence immunoassay (CLIA) method to detect antibodies against porcine parvovirus has been developed. Horseradish peroxidase (HRP) and the detection antibody were simultaneously co-immobilized on the surface of gold nanoparticles using the electrostatic method to form gold nanoparticle-based nanoprobes. This nanoprobe was employed in a sandwich-type CLIA, which enables CL signal readout from enzymatic catalysis and results in signal amplification. The presence of porcine parvovirus infection was determined in porcine parvovirus antibodies by measuring the CL intensity caused by the reaction of HRP-luminol with H2 O2 . Under optimal conditions, the obtained calibration plot for the standard positive serum was approximately linear within the dilution range of 1:80 to 1:5120. The limit of detection for the assay was 1:10,240 (S/N = 3), which is much lower than that typically achieved with an enzyme-linked immunosorbent assay (1:160; S/N = 3). A series of repeatability measurements using 1:320-fold diluted standard positive serum gave reproducible results with a relative standard deviation of 4.9% (n = 11). The ability of the immunosensor to analyze clinical samples was tested on porcine sera. The immunosensor had an efficiency of 90%, a sensitivity of 93.3%, and a specificity of 87.5% relative to the enzyme-linked immunosorbent assay results. Copyright © 2013 John Wiley & Sons, Ltd.

Determination of Chlorine in Milk via Molecular Absorption of SrCl Using High-Resolution Continuum Source Graphite Furnace Atomic Absorption Spectrometry.

PubMed

Ozbek, Nil; Akman, Suleyman

2016-07-20

Total chlorine in milk was determined via the molecular absorption of diatomic strontium monochloride at 635.862 nm using high-resolution continuum source graphite furnace atomic absorption spectrometry. The effects of coating the graphite furnace, using different modifiers, amount of molecule-forming element, and different calibrants were investigated and optimized. Chlorine concentrations in milk samples were determined in a Zr-coated graphite furnace using 25 μg of Sr as the molecule-forming reagent and applying a pyrolysis temperature of 600 °C and a molecule-forming temperature of 2300 °C. Linearity was maintained up to 500 μg mL(-1) of Cl. The method was tested by analyzing a certified reference wastewater. The results were in the uncertainty limits of the certified value. The limit of detection of the method was 1.76 μg mL(-1). The chlorine concentrations in various cow milk samples taken from the market were found in the range of 588-1472 mg L(-1).

Validated spectrofluorimetric method for the determination of carbamazepine in pharmaceutical dosage forms after reaction with 4-chloro-7--nitrobenzo-2-oxa-1,3-diazole (NBD-Cl).

PubMed

Walash, Mohammed I; El-Enany, Nahed; Askar, Hanany

2015-11-01

A sensitive and simple spectrofluorimetric method has been developed and validated for the determination of the anti-epileptic drug carbamazepine (CBZ) in its dosage forms. The method was based on a nucleophilic substitution reaction of CBZ with 4-chloro-7-nitrobenzo-2-oxa-1,3-diazole (NBD-Cl) in borate buffer (pH 9) to form a highly fluorescent derivative that was measured at 530 nm after excitation at 460 nm. Factors affecting the formation of the reaction product were studied and optimized, and the reaction mechanism was postulated. The fluorescence-concentration plot is rectilinear over the range of 0.6-8 µg/mL with limit of detection of 0.06 µg/mL and limit of quantitation of 0.19 µg/mL. The method was applied to the analysis of commercial tablets and the results were in good agreement with those obtained using the reference method. Validation of the analytical procedures was evaluated according to ICH guidelines. Copyright © 2015 John Wiley & Sons, Ltd.

Groundwater flowpaths and residence times inferred by 14C, 36Cl and 4He isotopes in the Continental Intercalaire aquifer (North-Western Africa)

NASA Astrophysics Data System (ADS)

Petersen, J. O.; Deschamps, P.; Hamelin, B.; Fourré, E.; Gonçalvès, J.; Zouari, K.; Guendouz, A.; Michelot, J.-L.; Massault, M.; Dapoigny, A.; ASTER Team

2018-05-01

In a semi-arid to arid climate context, dependency on groundwater resources may lead to overexploitation and deterioration of water quality. The Continental Intercalaire (CI) aquifer is one such continental-scale aquifer (more than a million of km2), which is mainly confined, poorly recharged but intensely abstracted. To date, the management of this resource relies on hydrogeological modelling and key parameters such as recharge/discharge rate and groundwater dynamics. We use a combination of residence time indicators (14C, 36Cl, 4He) and stable isotopes of water (2H and 18O) to give greater constraint on the groundwater residence time in the CI. In previous studies, 14C measurements and steady state modelling indicate a residence time of less than 100 ka whereas in others, 36Cl measurements and transient scenarios modelling suggest a longer residence time (>500 ka). In this study, most of the 14C measurements are below the limit of detection, establishing residence times greater than 40 ka and confirming the necessity of strict sampling protocols to exclude all air and AMS measurements when low 14C concentrations are expected. In the Tunisian recharge area, detectable 14C indicate sporadic recharge episodes (3-7 ka and 29-43 ka), whereas 4He and 36Cl concentrations in central areas suggest very old (<2 Ma) groundwaters. In these central areas, chlorine concentration can reach more than 2 g/l. Since 36Cl concentrations are up to 4 time less than the initial input, we are confident there is no excessive deep 36Cl production. We characterise five distinct flowpaths reaching the Tunisian discharge area using their isotopic signatures. According to our mixing model, the average contribution from the main recharge area, the Algerian Atlas Mountains, is around 88%. This value is close to hydrogeological models. Conversely, the contribution from the Dahar Mountains is lower than in the hydrogeological modelling (2% against 10%) whereas the Tinhert shows a greater contribution (10% against 1%). Increase of abstraction from the CI can potentially activate the circulation of old brackish groundwaters and dramatically decrease the water quality in the whole system.

Molecular and morphological characterization of Acanthamoeba isolated from corneal scrapes and contact lens wearers in Argentina.

PubMed

Casero, Rodolfo D; Mongi, Florencia; Laconte, Laura; Rivero, Fernando; Sastre, Dario; Teherán, Aníbal; Herrera, Giovanny; Ramírez, Juan David

2017-10-01

In this study, we describe the frequency of Acanthamoeba keratitis (AK) in patients that assisted in the Ophthalmology Department and determine the species/genotypes of free living amoebas (FLA) isolates. FLA from Corneal scrapes (CS) and contact lens (CL) wearers were studied by morphological and molecular characterization. A database was constructed with sociodemographic, clinical findings and history of use of CL variables. During January 2000 and September 2016 patients with corneal pathology admitted to the Ophthalmology Service of the University Hospital in Córdoba city, Argentina were included in the study. FLA were detected in 1.5% (11/739) and in 17% (11/65) of CS and CL analyzed respectively. FLA isolates from CL users evidenced an 80.9% of inappropriate lens maintenance, 4.8% (1/21) were not CL users that have been in contact with waters in outdoor environment and 14,3% (3/21) with no data about CL users. Acanthamoeba was confirmed in 100% and 82% of CS and LC respectively. The most frequent symptom associated with AK was red eye and photophobia. FLA from CS belonged to group II but 82% (9/11) and 18% (2/11) from CL belonged to group II and III respectively. T4 genotype and A. polyphaga species were detected in 100% of Acanthamoeba isolates. Poor CL hygiene practices, highlights the need for improved education about the severity of AK and consequences of improper CL hygiene. Genotype T4 detected in 100% of both CS and CL samples, consistently with previous findings indicating that this genotype is by far the most prevalent isolated from ocular infection. Copyright © 2017 Elsevier B.V. All rights reserved.

Elucidating the Structure-Reactivity Correlations of Phenothiazine-Based Fluorescent Probes toward ClO.

PubMed

Wang, Shichao; Zhang, Boyu; Wang, Wenjing; Feng, Gang; Yuan, Daqiang; Zhang, Xuanjun

2018-06-07

In this work, with the aim of developing effective molecular probes and investigating the structure-reactivity correlation, a short series of phenothiazine-based fluorescent probes are designed for the detection of ClO - with differing electron push-pull groups. Sensing experiment results and single-crystal X-ray analysis with the aid of time-dependent DFT (TD-DFT) calculations reveal that substituting groups with increasing electron-withdrawing ability can increase the dihedral angle of the phenothiazine moiety and reduce the gap energy of the probes, leading to enhanced reactivity toward ClO - . Both PT1 and PT2 show two-color switching upon detection of ClO - . PT1, with the strong electron-donating group thiophene, shows a fluorescence color switch from salmon to blue. PT2, with a medium electron-donating/accepting group benzothiazole, shows a fluorescence color switch from red to green. However, both PT1 and PT2 show almost no response to ONOO - . Through the introduction of strong electron-withdrawing ketone combined with a cyano group, PT3 shows a cyan emission upon detection of ClO - and weak red emission upon detection of ONOO - . HRMS and 1 H NMR results confirm that PT1 and PT2 have the same sensing mode, in which the divalent sulfur of phenothiazine can be oxidized to sulfoxide by ClO - . Upon reaction with ClO - , PT3 experiences two-step reactions. It is first oxidized into the sulfone structure by ClO - , and then transformed into sulfoxide phenothiazine aldehyde. Upon encountering ONOO - , PT3 changes into an aldehyde structure and some nonfluorescent byproducts. Owing to their special selectivity and high sensitivity, PT1 and PT2 are applied to image the endogenous ClO - in macrophage cells and zebrafish larvae. This study is expected to provide useful guidelines for probe design for various applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Detection of orbicularis oris muscle defects in first degree relatives of cleft lip children using ultrasound.

PubMed

Mittal, M; Maheshwari, N; Ahlawat, K; Sharma, V; Sultan, A; Chopra, R

2012-01-01

The severity of cleft lip (CL) varies considerably from complete bilateral CL and palate at one end of the spectrum to a minimal CL at the other. In some cases of microform clefting, there may be no visible manifestation of the defect on the lip surface (i.e., the defect is occult) and no residual functional deficit. This study used high resolution ultrasonography to detect subclinical anomalies of orbicularis oris muscle (OOM) in first degree relatives of CL +- cleft palate children and compared it with controls. Thirty relatives of 25 children with non-syndromic CL or CL+ CP were identified for the study. Thirty subjects having negative family history of CL/P in three generations and absence of any minimal cleft features were taken as controls. Ultrasound scans of OOM of all the controls and relatives were taken. Statistical analysis was performed using standard χ2 tests with Yates correction. Defects were seen in 13.3% of relatives and no defects were seen in controls, this was not statistically significant. The data support the hypothesis that subclinical CL cases with subepithelial OOM defects do exist and Orbicularis oris discontinuities represent the mildest form of CL.

A highly fluorescent hydrophilic ionic liquid as a potential probe for the sensing of biomacromolecules.

PubMed

Chen, Xu-Wei; Liu, Jia-Wei; Wang, Jian-Hua

2011-02-17

With respect to the conventional imidazolium ionic liquids which generally create very weak fluorescence with quantum yields at extremely low levels of 0.005-0.02, a symmetrical hydrophilic ionic liquid 1,3-butylimidazolium chloride (BBimCl) was found to be highly fluorescent with λ(em) at 388 nm when excited at λ(ex) < 340 nm. The very high quantum yield of BBimCl in aqueous medium, derived to be 0.523 when excited at 315 nm, was attributed to its symmetrical plane conjugating structure. In the presence of hemoglobin, the fluorescence of BBimCl could be significantly quenched, resulting from the coordinating interaction between the iron atom in the heme group of hemoglobin and the cationic imidazolium moiety. This feature of the present hydrophilic ionic liquid makes it a promising fluorescence probe candidate for the sensitive sensing of hemoglobin. A linear regression was observed within 3 × 10(-7) to 5 × 10(-6) mol L(-1) for hemoglobin, and a detection limit of 7.3 × 10(-8) mol L(-1) was derived.

Chemiluminescent Determination of Oxamyl in Drinking Water and Tomato Using Online Postcolumn UV Irradiation in a Chromatographic System.

PubMed

Murillo Pulgarín, José A; García Bermejo, Luisa F; Durán, Armando Carrasquero

2018-03-07

High-performance liquid chromatography (HPLC) was used to separate oxamyl from other pesticides in drinking water and tomato paste. The eluate emerging from the column tail was mixed with an alkaline solution of Co 2+ in EDTA and irradiated with UV light to induce photolysis of the carbamate in order to obtain free radicals and other reactive species that oxidize luminol and produce chemiluminescence (CL) as a result. The intensity of the CL signal was monitored in the form of chromatographic peaks. Under the optimum operating conditions for the HPLC-UV-CL system, the analyte concentration was linearly related to peak area. The limit of detection as determined in accordance with the IUPAC criterion was 0.17 mg L -1 . Oxamyl was successfully extracted with recoveries of 88.7-103.1% from spiked tomato paste by using a simple QuEChERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) sample preparation approach. Similar recoveries were obtained from drinking water samples spiked with oxamyl concentrations above the LOD. The proposed method is a simple, fast, accurate choice for quantifying this pesticide.

Quantitative Monitoring of Cefradine in Human Urine Using a Luminol/Sulfobutylether-β-Cyclodextrin Chemiluminescence System

NASA Astrophysics Data System (ADS)

Shen, M. X.; Tan, X. J.; Song, Zh. H.

2018-05-01

In this paper, a sensitive, rapid, and simple flow-injection chemiluminescence (FI-CL) technique is described for determining cefradine in human urine and capsule samples at the picogram level. The results show that cefradine within 0.1-100.0 nmol/L quantitatively quenches the CL intensity of the luminol/sulfo butylether-β-cyclodextrin (SBE-β-CD) system, with a relative correlation coefficient r of 0.9931. Subsequently, the possible mechanism for the quenching phenomenon is discussed in detail using the FI-CL and molecular docking methods. The proposed CL method, with a detection limit of 0.03 nmol/L (3σ) and relative standard deviations <3.0% (N = 7), is then implemented to monitor the excretion of cefradine in human urine. After orally administration, the cefradine reaches a maximum value of 1.37 ± 0.02 mg/mL at 2.0 h in urine, and the total excretion is 4.41 ± 0.03 mg/mL within 8.0 h. The absorption rate constant ka, the elimination rate constant ke, and the half-life t1/2 are 0.670 ± 0.008 h-1, 0.744 ± 0.005 h-1, and 0.93 ± 0.05 h, respectively.

New Accurate Wavenumbers of H35Cl^+ and H37Cl^+ Rovibrational Transitions in the v=0-1 Band of the ^2Π State.

NASA Astrophysics Data System (ADS)

Domenech, Jose Luis; Cueto, Maite; Herrero, Victor Jose; Tanarro, Isabel; Cernicharo, Jose; Drouin, Brian

2015-06-01

HCl^+ is a key intermediate in the interstellar chemistry of chlorine. It has been recently identified in space from Herschel's spectra and it has also been detected in the laboratory through its optical emission, infrared and mm-wave spectra. Now that Hershchel is decomissioned, further astrophysical studies on this radical ion will likely rely on ground-based observations in the mid-infrared. We have used a difference frequency laser spectrometer coupled to a hollow cathode discharge to measure the absorption spectrum of H35Cl^+ and H37Cl^+ in the v=0-1 band of the ^2Π state with Dopppler limited resolution. The accuracy of the individual measurements (˜ 10 MHz (3σ)) relies on a solid state wavemeter referenced to an iodine-stabilized Ar^+ laser. The new data are being fit using the CALPGM software from JPL, and the current status will be presented. M. De Luca et al., Astrophys. J. Lett. 751, L37 (2012) W. D. Sheasley and C. W. Mathews, J. Mol. Spectrosc. 47, 420 (1973) P. B. Davies, P. A. Hamilton, B. A. Johnson, Mol. Phys. 57, 217 (1986) H. Gupta, B. J. Drouin, and J. C. Pearson, Astrophys. J. Lett. 751, L37 (2012)

Non-covalently anchored multi-walled carbon nanotubes with hexa-decafluorinated zinc phthalocyanine as ppb level chemiresistive chlorine sensor

NASA Astrophysics Data System (ADS)

Sharma, Anshul Kumar; Mahajan, Aman; Bedi, R. K.; Kumar, Subodh; Debnath, A. K.; Aswal, D. K.

2018-01-01

A cost effective solution assembly method has been explored for preparing zinc(II)1,2,3,4,8,9,10,11,15,16,17,18,22,23,24,25-hexa-decafluoro-29H,31H-phthalocyanine/multi-walled carbon nanotubes (F16ZnPc/MWCNTs-COOH) hybrid. Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, transmission electron microscopy (TEM) and field emission scanning electron microscopy (FE-SEM) investigations confirm the non-covalent anchoring of F16ZnPc onto MWCNTs-COOH through п-п stacking interactions. Further, a highly sensitive and selective chemiresistive Cl2 sensor has been fabricated using F16ZnPc/MWCNTs-COOH hybrid. The response of sensor is found to be 21.28% for 2 ppm of Cl2 with a response time of 14 s and theoretical detection limit of the sensor is found down to 0.06 ppb. The improved Cl2 sensing characteristics of hybrid are found to be originated from the synergetic interaction between F16ZnPc and MWCNTs-COOH. The underlying mechanism for improved gas sensing performance of F16ZnPc/MWCNTs-COOH sensor towards Cl2 has been explained using Raman, X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS) studies.

Metagenomics of Microbial Communities in Gallbladder Bile from Patients with Gallbladder Cancer or Cholelithiasis

PubMed

Tsuchiya, Yasuo; Loza, Ernest; Villa-Gomez, Guido; Trujillo, Carlos C; Baez, Sergio; Asai, Takao; Ikoma, Toshikazu; Endoh, Kazuo; Nakamura, Kazutoshi

2018-04-25

Salmonella typhi and Helicobacter infections have been shown to increase risk of gallbladder cancer (GBC), but findings have been inconsistent. Other bacterial infections may also be associated with GBC. However, information on microbial pathogens in gallbladder bile of GBC patients is scarce. We aimed to investigate the microbial communities in gallbladder bile of patients with GBC and cholelithiasis (CL). Seven GBC patients and 30 CL patients were enrolled in this study. Genomic DNA was extracted from bile and the V3-V4 region of 16S rRNA was amplified. The sequencing results were compared with the 16S database, and the bacteria were identified by homology searches and phylogenetic analysis. DNA was detected in the bile of three GBC (42.9%; Bolivia, 1; Chile, 2) and four CL patients (13.3%; Bolivia, 1; Chile, 3). Of the 37 patients, 30 (81.1%) were negative and unable to analyze. Salmonella typhi and Helicobacter sp. were not detected in bile from any GBC patients. As the predominant species, Fusobacterium nucleatum, Escherichia coli, and Enetrobacter sp. were detected in bile from GBC patients. Those in bile from CL patients were Escherichia coli, Salmonella sp., and Enerococcus gallinarum. Escherichia coli was detected in bile samples from both GBC and CL patients. Whether the bacteria detected in bile from GBC patients would associated with the development of GBC warrant further investigation. Creative Commons Attribution License

Atmospheric trace gas analysis using matrix isolation-Fourier Transform Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Griffith, David W. T.; Schuster, Gerhard

1987-03-01

A novel cryogenic sampling method combining the matrix isolation technique with FTIR spectroscopy has been developed for atmospheric trace gas analysis. It is applicable to a wide range of molecules with detection limits typically in the 10-50 ppt range. The method is described along with some measurements of N2O, CFCl3, CF2Cl2, OCS, CS2, SO2 and PAN from samples collected at ground level and from an aircraft between 9 and 14 km.

Evaluation of neuraminidase enzyme assays using different substrates to measure susceptibility of influenza virus clinical isolates to neuraminidase inhibitors: report of the neuraminidase inhibitor susceptibility network.

PubMed

Wetherall, N T; Trivedi, T; Zeller, J; Hodges-Savola, C; McKimm-Breschkin, J L; Zambon, M; Hayden, F G

2003-02-01

The increasing use of influenza virus neuraminidase (NA) inhibitors (NIs) necessitates the development of reliable methods for assessing the NI susceptibility of clinical isolates. We evaluated three NA inhibition assays against a panel of five clinical isolates each of influenza virus A/H1N1, A/H3N2, and B strains and four viruses with a defined resistance genotype (R292K, H274Y, R152K, and E119V). For fluorometric enzyme assay (FA) 1 (FA-1), 2'-(4-methylumbelliferyl)-alpha-D-N-acetylneuraminic acid (MUNANA) at 100 microM was used as the substrate, with pretitration of the virus input. For FA-2, MUNANA at 200 microM was used as the substrate, with a fixed 1:10 dilution of input virus. For the chemiluminescence (CL) assay, the 1,2-dioxetane derivative of sialic acid at 100 microM was used as the substrate, with pretitration of the virus. Four different operators repeated the assays several times in a blinded fashion with both zanamivir and oseltamivir carboxylate (GS4071) to determine intra- and interassay variations. Mean 50% inhibitory concentration (IC(50)) values were lower and generally less variable with the CL assay. FA-1 displayed greater variation than the CL assay or FA-2 and the highest IC(50) values with zanamivir; FA-2 showed the highest values with oseltamivir, particularly for influenza virus B, and was more variable with zanamivir than was the CL assay. All three assays detected 40-fold or greater changes in IC(50) values for the resistant viruses with at least one drug. Mixing experiments, whereby increasing fractions (0, 20, 40, 60, 80, and 100%) of NA from a known NI-resistant virus were mixed with the corresponding NI-sensitive parental NA, indicated that the resolution of IC(50) values was clearer with the CL assay than with FA-2 for two of the resistant variants (R152K and E119V). The FA and CL methods were reliable for the detection of NI resistance, but all assays have certain limitations. Based on reproducibility, ease of automation, time required for the assay, and greater sensitivity, the CL assay was selected for future susceptibility testing of influenza virus isolates circulating globally.

Characterization of LIBS emission lines for the identification of chlorides, carbonates, and sulfates in salt/basalt mixtures for the application to MSL ChemCam data: LIBS OF CL, C, S IN SALT-BASALT MIXTURES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderson, D. E.; Ehlmann, B. L.; Forni, O.

Ancient environmental conditions on Mars can be probed through the identification of minerals on its surface, including water-deposited salts and cements dispersed in the pore space of sedimentary rocks. Laser-induced breakdown spectroscopy (LIBS) analyses by the Martian rover Curiosity's ChemCam instrument can indicate salts, and ChemCam surveys aid in identifying and selecting sites for further, detailed in situ analyses. Here, we performed laboratory LIBS experiments under simulated Mars conditions with a ChemCam-like instrument on a series of mixtures containing increasing concentrations of salt in a basaltic background to investigate the potential for identifying and quantifying chloride, carbonate, and sulfate saltsmore » found only in small amounts, dispersed in bulk rock with ChemCam, rather than concentrated in veins. The data then indicate that the presence of emission lines from the basalt matrix limited the number of Cl, C, and S emission lines found to be useful for quantitative analysis; nevertheless, several lines with intensities sensitive to salt concentration were identified. Detection limits for the elements based on individual emission lines ranged from ~20 wt % carbonate (2 wt % C), ~5–30 wt % sulfate (1–8 wt % S), and ~5–10 wt % chloride (3–6 wt % Cl) depending on the basaltic matrix and/or salt cation. Absolute quantification of Cl, C, and S in the samples via univariate analysis depends on the cation-anion pairing in the salt but appears relatively independent of matrices tested, following normalization. Our results are promising for tracking relative changes in the salt content of bulk rock on the Martian surface with ChemCam.« less

Characterization of LIBS emission lines for the identification of chlorides, carbonates, and sulfates in salt/basalt mixtures for the application to MSL ChemCam data: LIBS OF CL, C, S IN SALT-BASALT MIXTURES

DOE PAGES

Anderson, D. E.; Ehlmann, B. L.; Forni, O.; ...

2017-04-24

Ancient environmental conditions on Mars can be probed through the identification of minerals on its surface, including water-deposited salts and cements dispersed in the pore space of sedimentary rocks. Laser-induced breakdown spectroscopy (LIBS) analyses by the Martian rover Curiosity's ChemCam instrument can indicate salts, and ChemCam surveys aid in identifying and selecting sites for further, detailed in situ analyses. Here, we performed laboratory LIBS experiments under simulated Mars conditions with a ChemCam-like instrument on a series of mixtures containing increasing concentrations of salt in a basaltic background to investigate the potential for identifying and quantifying chloride, carbonate, and sulfate saltsmore » found only in small amounts, dispersed in bulk rock with ChemCam, rather than concentrated in veins. The data then indicate that the presence of emission lines from the basalt matrix limited the number of Cl, C, and S emission lines found to be useful for quantitative analysis; nevertheless, several lines with intensities sensitive to salt concentration were identified. Detection limits for the elements based on individual emission lines ranged from ~20 wt % carbonate (2 wt % C), ~5–30 wt % sulfate (1–8 wt % S), and ~5–10 wt % chloride (3–6 wt % Cl) depending on the basaltic matrix and/or salt cation. Absolute quantification of Cl, C, and S in the samples via univariate analysis depends on the cation-anion pairing in the salt but appears relatively independent of matrices tested, following normalization. Our results are promising for tracking relative changes in the salt content of bulk rock on the Martian surface with ChemCam.« less

Prospects for measuring cosmic microwave background spectral distortions in the presence of foregrounds

NASA Astrophysics Data System (ADS)

Abitbol, Maximilian H.; Chluba, Jens; Hill, J. Colin; Johnson, Bradley R.

2017-10-01

Measurements of cosmic microwave background (CMB) spectral distortions have profound implications for our understanding of physical processes taking place over a vast window in cosmological history. Foreground contamination is unavoidable in such measurements and detailed signal-foreground separation will be necessary to extract cosmological science. In this paper, we present Markov chain Monte Carlo based spectral distortion detection forecasts in the presence of Galactic and extragalactic foregrounds for a range of possible experimental configurations, focusing on the Primordial Inflation Explorer (PIXIE) as a fiducial concept. We consider modifications to the baseline PIXIE mission (operating ≃ 12 months in distortion mode), searching for optimal configurations using a Fisher approach. Using only spectral information, we forecast an extended PIXIE mission to detect the expected average non-relativistic and relativistic thermal Sunyaev-Zeldovich distortions at high significance (194σ and 11σ, respectively), even in the presence of foregrounds. The ΛCDM Silk damping μ-type distortion is not detected without additional modifications of the instrument or external data. Galactic synchrotron radiation is the most problematic source of contamination in this respect, an issue that could be mitigated by combining PIXIE data with future ground-based observations at low frequencies (ν ≲ 15-30 GHz). Assuming moderate external information on the synchrotron spectrum, we project an upper limit of |μ| < 3.6 × 10-7 (95 per cent c.l.), slightly more than one order of magnitude above the fiducial ΛCDM signal from the damping of small-scale primordial fluctuations, but a factor of ≃250 improvement over the current upper limit from COBE/Far Infrared Absolute Spectrophotometer. This limit could be further reduced to |μ| < 9.4 × 10-8 (95 per cent c.l.) with more optimistic assumptions about extra low-frequency information and would rule out many alternative inflation models and provide new constraints on decaying particle scenarios.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harrington, Timothy D.; Babauta, Jerome T.; Davenport, Emily K.

We investigated ion transport limitations on 3D graphite felt electrodes by growing Geobacter sulfurreducens biofilms with advection to eliminate external mass transfer limitations. We characterized ion transport limitations by: (i) showing that serially increasing NaCl concentration up to 200mM increased current linearly up to a total of þ273% vs. 0mM NaCl under advective conditions; (ii) growing the biofilm with a starting concentration of 200mM NaCl, which led to a maximum current increase of 400% vs. current generation without NaCl, and (iii) showing that un-colonized surface area remained even after steadystate current was reached. After accounting for iR effects, we confirmedmore » that the excess surface area existed despite a non-zero overpotential. The fact that the biofilm was constrained from colonizing and producing further current under these conditions confirmed the biofilms under study here were ion transport-limited. Our work demonstrates that the use of high surface area electrodes may not increase current density when the system design allows ion transport limitations to become dominant.« less

A highly selective chemiluminescent probe for the detection of chromium(VI)

NASA Astrophysics Data System (ADS)

Jin, Yan; Sun, Yonghua; Li, Chongying; Yang, Chao

2018-03-01

In present work, rhodamine B hydrazide and rhodamine 6G hydrazide were synthesized and the chemiluminescence performance has been investigated. Based on the chemiluminescence of rhodamine 6G hydrazide-chromium(VI), a selective and sensitive method for the direct detection of chromium(VI) was developed. The chemiluminescence intensity was linearly related to the concentration of chromium(VI) in the range of 2.60 × 10- 8-8.00 × 10- 6 mol/L with a correlation coefficient of r = 0.998 and a detection limit of 1.4 × 10- 8 mol/L (S/N = 3). The results indicated rhodamine 6G hydrazide was an excellent chemiluminescent probe for chromium(VI) without reduction of chromium(VI) to chromium(III). A possible mechanism of CL emission was also suggested.

Enhanced amperometric detection of metronidazole in drug formulations and urine samples based on chitosan protected tetrasulfonated copper phthalocyanine thin-film modified glassy carbon electrode.

PubMed

Meenakshi, S; Pandian, K; Jayakumari, L S; Inbasekaran, S

2016-02-01

An enhanced electrocatalytic reduction of metronidazole antibiotic drug molecule using chitosan protected tetrasulfonated copper phthalocyanine (Chit/CuTsPc) thin-film modified glassy carbon electrode (GCE) has been developed. An irreversible reduction occurs at -0.47V (vs. Ag/AgCl) using Chit/CuTsPc modified GCE. A maximum peak current value is obtained at pH1 and the electrochemical reduction reaction is a diffusion controlled one. The detection limit is found to be 0.41nM from differential pulse voltammetry (DPV) method. This present investigation method is adopted for electrochemical detection of metronidazole in drug formulation and urine samples by using DPV method. Copyright © 2015 Elsevier B.V. All rights reserved.

Detection of adenosine triphosphate through polymerization-induced aggregation of actin-conjugated gold/silver nanorods.

PubMed

Liao, Yu-Ju; Shiang, Yen-Chun; Chen, Li-Yi; Hsu, Chia-Lun; Huang, Chih-Ching; Chang, Huan-Tsung

2013-11-08

We have developed a simple and selective nanosensor for the optical detection of adenosine triphosphate (ATP) using globular actin-conjugated gold/silver nanorods (G-actin-Au/Ag NRs). By simply mixing G-actin and Au/Ag NRs (length ~56 nm and diameter ~12 nm), G-actin-Au/Ag NRs were prepared which were stable in physiological solutions (25 mM Tris-HCl, 150 mM NaCl, 5.0 mM KCl, 3.0 mM MgCl2 and 1.0 mM CaCl2; pH 7.4). Introduction of ATP into the G-actin-Au/Ag NR solutions in the presence of excess G-actin induced the formation of filamentous actin-conjugated Au/Ag NR aggregates through ATP-induced polymerization of G-actin. When compared to G-actin-modified spherical Au nanoparticles having a size of 13 nm or 56 nm, G-actin-Au/Ag NRs provided better sensitivity for ATP, mainly because the longitudinal surface plasmon absorbance of the Au/Ag NR has a more sensitive response to aggregation. This G-actin-Au/Ag NR probe provided high sensitivity (limit of detection 25 nM) for ATP with remarkable selectivity (>10-fold) over other adenine nucleotides (adenosine, adenosine monophosphate and adenosine diphosphate) and nucleoside triphosphates (guanosine triphosphate, cytidine triphosphate and uridine triphosphate). It also allowed the determination of ATP concentrations in plasma samples without conducting tedious sample pretreatments; the only necessary step was simple dilution. Our experimental results are in good agreement with those obtained from a commercial luciferin-luciferase bioluminescence assay. Our simple, sensitive and selective approach appears to have a practical potential for the clinical diagnosis of diseases (e.g. cystic fibrosis) associated with changes in ATP concentrations.

Detection of adenosine triphosphate through polymerization-induced aggregation of actin-conjugated gold/silver nanorods

NASA Astrophysics Data System (ADS)

Liao, Yu-Ju; Shiang, Yen-Chun; Chen, Li-Yi; Hsu, Chia-Lun; Huang, Chih-Ching; Chang, Huan-Tsung

2013-11-01

We have developed a simple and selective nanosensor for the optical detection of adenosine triphosphate (ATP) using globular actin-conjugated gold/silver nanorods (G-actin-Au/Ag NRs). By simply mixing G-actin and Au/Ag NRs (length ˜56 nm and diameter ˜12 nm), G-actin-Au/Ag NRs were prepared which were stable in physiological solutions (25 mM Tris-HCl, 150 mM NaCl, 5.0 mM KCl, 3.0 mM MgCl2 and 1.0 mM CaCl2; pH 7.4). Introduction of ATP into the G-actin-Au/Ag NR solutions in the presence of excess G-actin induced the formation of filamentous actin-conjugated Au/Ag NR aggregates through ATP-induced polymerization of G-actin. When compared to G-actin-modified spherical Au nanoparticles having a size of 13 nm or 56 nm, G-actin-Au/Ag NRs provided better sensitivity for ATP, mainly because the longitudinal surface plasmon absorbance of the Au/Ag NR has a more sensitive response to aggregation. This G-actin-Au/Ag NR probe provided high sensitivity (limit of detection 25 nM) for ATP with remarkable selectivity (>10-fold) over other adenine nucleotides (adenosine, adenosine monophosphate and adenosine diphosphate) and nucleoside triphosphates (guanosine triphosphate, cytidine triphosphate and uridine triphosphate). It also allowed the determination of ATP concentrations in plasma samples without conducting tedious sample pretreatments; the only necessary step was simple dilution. Our experimental results are in good agreement with those obtained from a commercial luciferin-luciferase bioluminescence assay. Our simple, sensitive and selective approach appears to have a practical potential for the clinical diagnosis of diseases (e.g. cystic fibrosis) associated with changes in ATP concentrations.

Excess surface area in bioelectrochemical systems causes ion transport limitations.

PubMed

Harrington, Timothy D; Babauta, Jerome T; Davenport, Emily K; Renslow, Ryan S; Beyenal, Haluk

2015-05-01

We investigated ion transport limitations on 3D graphite felt electrodes by growing Geobacter sulfurreducens biofilms with advection to eliminate external mass transfer limitations. We characterized ion transport limitations by: (i) showing that serially increasing NaCl concentration up to 200 mM increased current linearly up to a total of +273% vs. 0 mM NaCl under advective conditions; (ii) growing the biofilm with a starting concentration of 200 mM NaCl, which led to a maximum current increase of 400% vs. current generation without NaCl, and (iii) showing that un-colonized surface area remained even after steady-state current was reached. After accounting for iR effects, we confirmed that the excess surface area existed despite a non-zero overpotential. The fact that the biofilm was constrained from colonizing and producing further current under these conditions confirmed the biofilms under study here were ion transport-limited. Our work demonstrates that the use of high surface area electrodes may not increase current density when the system design allows ion transport limitations to become dominant. © 2014 Wiley Periodicals, Inc.

Dysprosium-sensitized chemiluminescence system for the determination of enoxacin in pharmaceutical preparations and biological fluids with flow-injection sampling.

PubMed

Sun, Han-wen; Wu, Yuan-yuan; Li, Li-qing

2009-03-01

A novel trivalence dysprosium(Dy(3+))-sensitized chemiluminescence method was developed for the first time for the determination of enoxacin (ENX) using flow-injection sampling based on the chemiluminescence (CL) associated with the reaction of the Dy(3+)-cerium(Ce(IV))-S(2)O(3) (2-)-ENX system and the Dy(3+)-MnO(4) (-) S(2)O(3) (2-)-ENX system. The analytical conditions for CL emission were investigated and optimized. The relationship between the CL intensity of ENX and its concentration has good linearity, with a correlation coefficient of 0.9984-0.9994. The limit of detection (LOD, 3sigma) was 0.20 ng/mL for the Dy(3+)-ENX-S(2)O(3)(2-)-Ce(IV)-H(2)SO(4) system and 0.22 ng/mL for the Dy(3+)-ENX-S(2)O(3)(2-)-MnO(4) (-)-HNO(3) system. The relative standard deviation (RSD, n = 11) was 1.8% for 11 determinations of 60 ng/mL ENX. The proposed method was applied to the analysis of ENX in injections, serum and urine samples with a recovery of 98%-105%. A possible mechanism for this sensitized CL reaction is discussed by comparing the CL spectra with the fluorescence emission spectra. The proposed method represents a wide linear range, high sensitivity and accuracy, and can be used for the routine determination of ENX in pharmaceutical preparations and biological fluids. Copyright 2009 John Wiley & Sons, Ltd.

Chemiluminescence from an oxidation reaction of rhodamine B with cerium(IV) in a reversed micellar medium of cetyltrimethylammonium chloride in 1-hexanol-cyclohexane/water.

PubMed

Hasanin, Tamer H A; Tsunemine, Yusuke; Tsukahara, Satoshi; Okamoto, Yasuaki; Fujiwara, Terufumi

2011-01-01

The chemiluminescence (CL) emission, observed when rhodamine B (RB) in 1-hexanol-cyclohexane was mixed with cerium(IV) sulfate in sulfuric acid dispersed in a reversed micellar medium of cetyltrimethylammonium chloride (CTAC) in 1-hexanol-cyclohexane/water, was investigated using a flow-injection system. The CL emission from the oxidation reaction of RB with Ce(IV) was found to be stronger in the CTAC reversed micellar solution compared with an aqueous solution. Bearing on the enhancement effect of the CTAC reverse micelles on the RB-Ce(IV) CL, several studies including stopped-flow, fluorescence and electron spin resonance (ESR) spectrometries were performed. Rapid spectral changes of an intermediate in the RB-Ce(IV) reaction in the aqueous and reversed micellar solutions were successfully observed using a stopped-flow method. The effect of the experimental variables, i.e., oxidant concentration, sulfuric acid concentration, the mole fraction of 1-hexanol, water-to-surfactant molar concentration ratio, flow rate, upon the CL intensity was evaluated. Under the experimental conditions optimized for a flow-injection determination of RB based on the new reversed micellar-mediated CL reaction with Ce(IV), a detection limit of 0.08 µmol dm(-3) RB was achieved, and a linear calibration graph was obtained with a dynamic range from 0.5 to 20 µmol dm(-3). The relative standard deviation (n = 6) obtained at an RB concentration of 3 µmol dm(-3) was 3%.

Evaluation of a contact lens-embedded sensor for intraocular pressure measurement.

PubMed

Twa, Michael D; Roberts, Cynthia J; Karol, Huikai J; Mahmoud, Ashraf M; Weber, Paul A; Small, Robert H

2010-08-01

To evaluate a novel contact lens-embedded pressure sensor for continuous measurement of intraocular pressure (IOP). Repeated measurements of IOP and ocular pulse amplitude (OPA) were recorded in 12 eyes of 12 subjects in sitting and supine positions using 3 configurations of the dynamic contour tonometer: slit-lamp mounted (DCT), hand-held (HH), and contact lens-embedded sensor (CL). The IOP and OPA for each condition were compared using repeated measures ANOVA and the 95% limits of agreement were calculated. The sitting IOP (mean and 95% CI) for each configuration was DCT: 16.3 mm Hg (15.6 to 17.1 mm Hg), HH: 16.6 mm Hg (15.6 to 17.6 mm Hg), and CL: 15.7 mm Hg (15 to 16.3 mm Hg). The sitting OPA for each configuration was DCT: 2.4 mm Hg (2.1 to 2.6 mm Hg), HH: 2.4 mm Hg (2.1 to 2.7 mm Hg), and CL: 2.1 mm Hg (1.8 to 2.3 mm Hg). Supine IOP and OPA measurements with the CL and HH sensors were both greater than their corresponding sitting measurements, but were significantly less with the CL sensor than the HH sensor. The mean difference and 95% Limits of Agreement were smallest for the DCT and CL sensor comparisons (0.7+/-3.9 mm Hg) and widest for the CL and HH sensors (-1.9+/-7.25 mm Hg); these wider limits were attributed to greater HH measurement variability. The CL sensor was comparable to HH and DCT sensors with sitting subjects and is a viable method for measuring IOP and OPA. Supine measurements of IOP and OPA were greater than sitting conditions and were comparatively lower with the CL sensor. HH measurements were more variable than CL measurements and this influenced the Limits of Agreement for both sitting and supine conditions.

First limits on the very-high energy gamma-ray afterglow emission of a fast radio burst. H.E.S.S. observations of FRB 150418

NASA Astrophysics Data System (ADS)

H.E.S.S. Collaboration; Abdalla, H.; Abramowski, A.; Aharonian, F.; Ait Benkhali, F.; Akhperjanian, A. G.; Andersson, T.; Angüner, E. O.; Arakawa, M.; Arrieta, M.; Aubert, P.; Backes, M.; Balzer, A.; Barnard, M.; Becherini, Y.; Becker Tjus, J.; Berge, D.; Bernhard, S.; Bernlöhr, K.; Blackwell, R.; Böttcher, M.; Boisson, C.; Bolmont, J.; Bordas, P.; Bregeon, J.; Brun, F.; Brun, P.; Bryan, M.; Büchele, M.; Bulik, T.; Capasso, M.; Carr, J.; Casanova, S.; Cerruti, M.; Chakraborty, N.; Chalme-Calvet, R.; Chaves, R. C. G.; Chen, A.; Chevalier, J.; Chrétien, M.; Coffaro, M.; Colafrancesco, S.; Cologna, G.; Condon, B.; Conrad, J.; Cui, Y.; Davids, I. D.; Decock, J.; Degrange, B.; Deil, C.; Devin, J.; Dewilt, P.; Dirson, L.; Djannati-Ataï, A.; Domainko, W.; Donath, A.; Drury, L. O.'c.; Dutson, K.; Dyks, J.; Edwards, T.; Egberts, K.; Eger, P.; Ernenwein, J.-P.; Eschbach, S.; Farnier, C.; Fegan, S.; Fernandes, M. V.; Fiasson, A.; Fontaine, G.; Förster, A.; Funk, S.; Füßling, M.; Gabici, S.; Gajdus, M.; Gallant, Y. A.; Garrigoux, T.; Giavitto, G.; Giebels, B.; Glicenstein, J. F.; Gottschall, D.; Goyal, A.; Grondin, M.-H.; Hahn, J.; Haupt, M.; Hawkes, J.; Heinzelmann, G.; Henri, G.; Hermann, G.; Hervet, O.; Hinton, J. A.; Hofmann, W.; Hoischen, C.; Holler, M.; Horns, D.; Ivascenko, A.; Iwasaki, H.; Jacholkowska, A.; Jamrozy, M.; Janiak, M.; Jankowsky, D.; Jankowsky, F.; Jingo, M.; Jogler, T.; Jouvin, L.; Jung-Richardt, I.; Kastendieck, M. A.; Katarzyński, K.; Katsuragawa, M.; Katz, U.; Kerszberg, D.; Khangulyan, D.; Khélifi, B.; Kieffer, M.; King, J.; Klepser, S.; Klochkov, D.; Kluźniak, W.; Kolitzus, D.; Komin, Nu.; Kosack, K.; Krakau, S.; Kraus, M.; Krüger, P. P.; Laffon, H.; Lamanna, G.; Lau, J.; Lees, J.-P.; Lefaucheur, J.; Lefranc, V.; Lemière, A.; Lemoine-Goumard, M.; Lenain, J.-P.; Leser, E.; Lohse, T.; Lorentz, M.; Liu, R.; López-Coto, R.; Lypova, I.; Marandon, V.; Marcowith, A.; Mariaud, C.; Marx, R.; Maurin, G.; Maxted, N.; Mayer, M.; Meintjes, P. J.; Meyer, M.; Mitchell, A. M. W.; Moderski, R.; Mohamed, M.; Mohrmann, L.; Morå, K.; Moulin, E.; Murach, T.; Nakashima, S.; de Naurois, M.; Niederwanger, F.; Niemiec, J.; Oakes, L.; O'Brien, P.; Odaka, H.; Öttl, S.; Ohm, S.; Ostrowski, M.; Oya, I.; Padovani, M.; Panter, M.; Parsons, R. D.; Pekeur, N. W.; Pelletier, G.; Perennes, C.; Petrucci, P.-O.; Peyaud, B.; Piel, Q.; Pita, S.; Poon, H.; Prokhorov, D.; Prokoph, H.; Pühlhofer, G.; Punch, M.; Quirrenbach, A.; Raab, S.; Reimer, A.; Reimer, O.; Renaud, M.; de Los Reyes, R.; Richter, S.; Rieger, F.; Romoli, C.; Rowell, G.; Rudak, B.; Rulten, C. B.; Sahakian, V.; Saito, S.; Salek, D.; Sanchez, D. A.; Santangelo, A.; Sasaki, M.; Schlickeiser, R.; Schüssler, F.; Schulz, A.; Schwanke, U.; Schwemmer, S.; Seglar-Arroyo, M.; Settimo, M.; Seyffert, A. S.; Shafi, N.; Shilon, I.; Simoni, R.; Sol, H.; Spanier, F.; Spengler, G.; Spies, F.; Stawarz, Ł.; Steenkamp, R.; Stegmann, C.; Stycz, K.; Sushch, I.; Takahashi, T.; Tavernet, J.-P.; Tavernier, T.; Taylor, A. M.; Terrier, R.; Tibaldo, L.; Tiziani, D.; Tluczykont, M.; Trichard, C.; Tsuji, N.; Tuffs, R.; Uchiyama, Y.; van der Walt, D. J.; van Eldik, C.; van Rensburg, C.; van Soelen, B.; Vasileiadis, G.; Veh, J.; Venter, C.; Viana, A.; Vincent, P.; Vink, J.; Voisin, F.; Völk, H. J.; Vuillaume, T.; Wadiasingh, Z.; Wagner, S. J.; Wagner, P.; Wagner, R. M.; White, R.; Wierzcholska, A.; Willmann, P.; Wörnlein, A.; Wouters, D.; Yang, R.; Zabalza, V.; Zaborov, D.; Zacharias, M.; Zanin, R.; Zdziarski, A. A.; Zech, A.; Zefi, F.; Ziegler, A.; Żywucka, N.; Superb Collaboration; Jankowski, F.; Keane, E. F.; Petroff, E.

2017-01-01

Aims: Following the detection of the fast radio burst FRB150418 by the SUPERB project at the Parkes radio telescope, we aim to search for very-high energy gamma-ray afterglow emission. Methods: Follow-up observations in the very-high energy gamma-ray domain were obtained with the H.E.S.S. imaging atmospheric Cherenkov telescope system within 14.5 h of the radio burst. Results: The obtained 1.4 h of gamma-ray observations are presented and discussed. At the 99% C.L. we obtained an integral upper limit on the gamma-ray flux of Φγ(E > 350 GeV) < 1.33 × 10-8 m-2 s-1. Differential flux upper limits as function of the photon energy were derived and used to constrain the intrinsic high-energy afterglow emission of FRB 150418. Conclusions: No hints for high-energy afterglow emission of FRB 150418 were found. Taking absorption on the extragalactic background light into account and assuming a distance of z = 0.492 based on radio and optical counterpart studies and consistent with the FRB dispersion, we constrain the gamma-ray luminosity at 1 TeV to L < 5.1 × 1047 erg/s at 99% C.L.

Label-free technology for the amplified detection of microRNA based on the allosteric hairpin DNA switch and hybridization chain reaction.

PubMed

Cai, Sheng; Cao, Zhijuan; Lau, Choiwan; Lu, Jianzhong

2014-11-21

By using the allosteric hairpin DNA switch, a novel assay for the detection of microRNA (miRNA) let-7a via a hybridization chain reaction (HCR) was introduced. Briefly, the hairpin DNA switch probe is a single-stranded DNA consisting of a streptavidin (SA) aptamer sequence, a target binding sequence and a certain sequence that acts as a trigger of the HCR. In the presence of target let-7a, the hairpin DNA switch would open and expose the stem region sequences, where a part of this sequence acts as initiator sequence strands for the HCR and triggers a cascade of hybridization events that yields nicked double helices analogous to alternating copolymers, another part is the SA aptamer sequence which activates its binding affinity to SA on SA-coated magnetic particles. The hybridization event could be sensitively detected via an instantaneous derivatization reaction between a special chemiluminescence (CL) reagent, 3,4,5-trimethoxylphenylglyoxal (TMPG) and the guanine nucleotides within the target, the hairpin DNA switch probe, and HCR helices to form an unstable CL intermediate for the generation of light. Our results show that the coupling of the hairpin DNA switch probe and the HCR for the amplified detection of let-7a achieves a better performance (e.g. wide linear response range: 0.1-1000 fmol, low detection limit: 0.1 fmol, and high specificity). Furthermore, this approach could be easily applied to the detection of let-7a in human lung cells, and extended to detect other types of miRNA and proteins such as PDGF based on aptamers. We believe such advancements will represent a significant step towards improved diagnostics and more personalized medical treatment.

Guanidinium ionic liquid-based surfactants as low cytotoxic extractants: Analytical performance in an in-situ dispersive liquid-liquid microextraction method for determining personal care products.

PubMed

Pacheco-Fernández, Idaira; Pino, Verónica; Ayala, Juan H; Afonso, Ana M

2018-07-20

The IL-based surfactant octylguanidinium chloride (C 8 Gu-Cl) was designed and synthetized with the purpose of obtaining a less harmful surfactant: containing guanidinium as core cation and a relatively short alkyl chain. Its interfacial and aggregation behavior was evaluated through conductivity and fluorescence measurements, presenting a critical micelle concentration value of 42.5 and 44.6mmolL -1 , respectively. Cytotoxicity studies were carried out with C 8 Gu-Cl and other IL-based and conventional surfactants, specifically the analogue 1-octyl-3-methylimidazolium chloride (C 8 MIm-Cl), and other imidazolium- (C 16 MIm-Br) and pyridinium- (C 16 Py-Cl) based surfactants, together with the conventional cationic CTAB and the conventional anionic SDS. From these studies, C 8 Gu-Cl was the only one to achieve the classification of low cytotoxicity. An in situ dispersive liquid-liquid microextraction (DLLME) method based on transforming the water-soluble C 8 Gu-Cl IL-based surfactant into a water-insoluble IL microdroplet via a simple metathesis reaction was then selected as the extraction/preconcentration method for a group of 6 personal care products (PCPs) present in cosmetic samples. The method was carried out in combination with high-performance liquid chromatography (HPLC) and diode array detection (DAD). The method was properly optimized, requiring the use of only 30μL of C 8 Gu-Cl for 10mL of aqueous sample with a NaCl content of 8% (w/v) to adjust the ionic strength and pH value of 5. The metathesis reaction required the addition of the anion exchange reagent (bis[(trifluoromethyl)sulfonyl]imide - 1:1 molar ratio), followed by vortex and centrifugation, and dilution of the final microdroplet up to 60μL with acetonitrile before the injection in the HPLC-DAD system. The optimum in situ DLLME-HPLC-DAD method takes ∼10min for the extraction step and ∼22min for the chromatographic separation, with analytical features of low detection limits: down to 0.4μgL -1 ; high reproducibility: with RSD values lower than 10% (intra-day) and 16% (inter-day) for a spiked level of 15μgL -1 ; and an average enrichment factor of 89. The requirement of low volumes (30μL) of a low cytotoxic IL-based surfactant allows the method to be considered less harmful than other common analytical microextraction approaches. Copyright © 2017 Elsevier B.V. All rights reserved.

Determination of manganese- and manganese-containing fungicides with lucigenin-Tween-20-enhanced chemiluminescence detection.

PubMed

Yaqoob, Mohammad; Asghar, Mohammad; Nabi, Abdul

2015-11-01

A flow-injection (FI) method is reported for the determination of Mn(II), maneb and mancozeb fungicides based on the catalytic effect of Mn(II) on the oxidation of lucigenin and dissolved oxygen in a basic solution. The Tween-20 surfactant has been reported for first time to enhance lucigenin chemiluminescence (CL) intensity in the presence of Mn(II) (53%) and maneb and mancozeb (89%). The calibration graphs were linear in the concentration range of 0.001-1.5 mg L(-1) (R(2) = 0.9982 (n = 11) with a limit of detection (S/N = 3) of 0.1 µg L(-1) for Mn(II) and 0.01-3.0 mg L(-1) [R(2) = 0.9989 and R(2) = 0.9992 (n = 6)] with a limit of detection (S/N =3) of 1.0 µg L(-1) for maneb and mancozeb respectively. Injection throughputs of 90 and 120 h(-1) for Mn(II) and maneb and mancozeb respectively, and relative standard deviations of 1.0-3.4% were obtained in the concentration range studied. The experimental variables, e.g., reagents concentrations, flow rates, sample volume, and photomultiplier tube voltage, were optimized and potential interferences were investigated. The analysis of Mn(II) in river water reference materials (SLRS-4 and SLRS-5) showed good agreement with the certified values incorporating an on-line 8-hydroxyquinoline chelating column in the manifold for removing interfering metal ions. Recoveries for maneb and mancozeb were in the range of 92 ± 5 to 104 ± 3% and 91 ± 2 to 100 ± 4% (n = 3) respectively. The effect of 30 other pesticides (fungicides, herbicides and insecticides) was also examined in the lucigenin-Tween-20 CL system. Copyright © 2015 John Wiley & Sons, Ltd.

Radiosynthesis and ex vivo evaluation of (R)-(-)-2-chloro-N-[1-11C-propyl]n-propylnorapomorphine.

PubMed

Palner, Mikael; McCormick, Patrick; Gillings, Nic; Begtrup, Mikael; Wilson, Alan A; Knudsen, Gitte M

2010-01-01

Several dopamine D(2) agonist radioligands have been used with positron emission tomography (PET), including [(11)C-]-(-)-MNPA, [(11)C-]-(-)-NPA and [(11)C]-(+)-PHNO. These radioligands are considered particularly powerful for detection of endogenous dopamine release, but they either provide PET brain images with limited contrast or have affinity for both D(2) and D(3) receptors. We here present the carbon-11 radiolabeling and ex vivo evaluation of 2-Cl-(-)-NPA, a novel PET-tracer candidate with high in vitro D(2)/D(3) selectivity. 2-Cl-[(11)C]-(-)-NPA and [(11)C]-(-)-NPA were synthesized by a two step N-acylation-reduction process using [(11)C]-propionyl chloride. Awake rats were injected with either tracer, via the tail vein. The rats were decapitated at various times, the brains were removed and quickly dissected, and plasma metabolites were measured. Radioligand specificity, and P-glycoprotein involvement in brain uptake, was also assessed. 2-Cl-[(11)C]-(-)-NPA and [(11)C]-(-)-NPA were produced in high specific activity and purity. 2-Cl-[(11)C]-(-)-NPA accumulated slower in the striatum than [(11)C]-(-)-NPA, reaching maximum concentrations after 30 min. The maximal striatal uptake of 2-Cl-[(11)C]-(-)-NPA (standard uptake value 0.72+/-0.24) was approximately half that of [(11)C]-(-)-NPA (standard uptake value 1.37+/-0.18). Nonspecific uptake was similar for the two compounds. 2-Cl-[(11)C]-(-)-NPA was metabolized quickly, leaving only 17% of the parent compound in the plasma after 30 min. The specific binding of 2-Cl-[(11)C]-(-)-NPA was completely blocked and inhibition of P-glycoprotein did not alter the brain uptake. Ex vivo experiments showed, despite a favorable D(2)/D(3) selectivity, that 2-Cl-[(11)C]-(-)-NPA is inferior to [(11)C]-(-)-NPA as a PET tracer in rat, because of slower brain uptake and lower specific to nonspecific binding ratio. Copyright 2010 Elsevier Inc. All rights reserved.

In situ quantification of Br and Cl in minerals and fluid inclusions by LA-ICP-MS: a powerful tool to identify fluid sources

USGS Publications Warehouse

Hammerli, Johannes; Rusk, Brian; Spandler, Carl; Emsbo, Poul; Oliver, Nicholas H.S.

2013-01-01

Bromine and chlorine are important halogens for fluid source identification in the Earth's crust, but until recently we lacked routine analytical techniques to determine the concentration of these elements in situ on a micrometer scale in minerals and fluid inclusions. In this study, we evaluate the potential of in situ Cl and Br measurements by LA-ICP-MS through analysis of a range of scapolite grains with known Cl and Br concentrations. We assess the effects of varying spot sizes, variable plasma energy and resolve the contribution of polyatomic interferences on Br measurements. Using well-characterised natural scapolite standards, we show that LA-ICP-MS analysis allows measurement of Br and Cl concentrations in scapolite, and fluid inclusions as small as 16 μm in diameter and potentially in sodalite and a variety of other minerals, such as apatite, biotite, and amphibole. As a demonstration of the accuracy and potential of Cl and Br analyses by LA-ICP-MS, we analysed natural fluid inclusions hosted in sphalerite and compared them to crush and leach ion chromatography Cl/Br analyses. Limit of detection for Br is ~8 μg g−1, whereas relatively high Cl concentrations (> 500 μg g−1) are required for quantification by LA-ICP-MS. In general, our LA-ICP-MS fluid inclusion results agree well with ion chromatography (IC) data. Additionally, combined cathodoluminescence and LA-ICP-MS analyses on natural scapolites within a well-studied regional metamorphic suite in South Australia demonstrate that Cl and Br can be quantified with a ~25 μm resolution in natural minerals. This technique can be applied to resolve a range of hydrothermal geology problems, including determining the origins of ore forming brines and ore deposition processes, mapping metamorphic and hydrothermal fluid provinces and pathways, and constraining the effects of fluid–rock reactions and fluid mixing.

Neuropathic pain and use of PainDETECT in patients with fibromyalgia: a cohort study.

PubMed

Gauffin, Jarno; Hankama, Tiina; Kautiainen, Hannu; Hannonen, Pekka; Haanpää, Maija

2013-02-14

Fibromyalgia has a plethorae of symptoms, which can be confusing and even misleading. Accurate evaluation is necessary when patients with fibromyalgia are treated. Different types of instruments are available for the clinicians to supplement evaluation. Our objective was to study the applicability of the PainDETECT instrument to screen neuropathic pain in patients with fibromyalgia. 158 patients with primary fibromyalgia underwent a neurological examination including bedside sensory testing. They also fulfilled four questionnaires: PainDETECT, Beck depression inventory IA (BDI IA), Fibromyalgia Impact Questionnaire (FIQ) and a self-made questionnaire regarding present pain and pain relieving methods of the patients. The results of the clinical evaluation and questionnaires were then compared. Clinically verified neuropathic pain was diagnosed in 53/158 [34% (95% Cl: 26 to 41)] patients. The ROC curve achieved a maximum Youden´s index at score of 17 when sensitivity was 0.79 (95% Cl: 0.66 to 0.89) and specificity 0.53 (95% Cl: 0.43 to 0.63). The PainDETECT total score (OR: 1.14 95% Cl: 1.06 to 1.22), FM as the worst current pain (OR: 0.31; 95% 0.16 to 0.62), body mass index (BMI) (OR: 1.05; 95% Cl: 1.00 to 1.11) and the intensity of current pain (OR: 1.20; 95% Cl: 1.01 to 1.41) were significantly associated with the presence of neuropathic pain in univariate analyses. This study highlights the importance of thorough clinical examination. The Neuropathic pain screening tool PainDETECT is not as useful in patients with fibromyalgia as in patients with uncompromised central pain control.

Kinetics of Semiconductor Surface Chemistry: Silicon Atomic Layer Processing

DTIC Science & Technology

1993-05-01

H20 --> Si-OH + HCI; and (B) Si-OH + SiCl4 -- > Si-O-SiCl 3 + HC1. We examined reaction (A) for SiO 2 growth on Si(111)7x7 and porous silicon and... SiCl4 > Si-O-SiCl3 + HCI Repeat... • Reaction (A) and (B) are self-limiting * Expect excellent conformality Si-Cl + H20 ->Si-OH + HC1 SiCl2 LITD

Synthesis of silver/silver chloride/graphene oxide composite and its surface-enhanced Raman scattering activity and self-cleaning property

NASA Astrophysics Data System (ADS)

Zhao, Nan; Fei, Xiao; Cheng, Xiaonong; Yang, Juan

2017-09-01

Recently, silver nanoparticles decorated with graphene and graphene oxide (GO) sheets can be employed as surface-enhanced Raman scattering (SERS) substrates. However, their SERS activity on macromolecular compound detection is all one-time process. In order to solve this issue and decrease the cost of routine SERS detection, silver/silver chloride (Ag/AgCl) with photocatalytic activity under visible light was introduced. In this study, a novel, simple and clean approach is carried out for synthesis of the Ag/AgCl/GO composite. The Ag/AgCl colloidal solution is obtained by hydrothermal method and then mixed with GO solution to obtain the Ag/AgCl/GO composite using a facile electrostatic self-assembly method. Results showed that the Ag/AgCl/GO composite has the optimized SERS activity to Rhodamine 6G molecules with the maximum enhancement factor value of 3.8×107. Furthermore, the Ag/AgCl particles with high efficient and stable photocatalytic activity under visible light lead to an outstanding self-cleaning property of the Ag/AgCl/GO composite.

Confocal filtering in cathodoluminescence microscopy of nanostructures

NASA Astrophysics Data System (ADS)

Narváez, Angela C.; Weppelman, I. Gerward C.; Moerland, Robert J.; Hoogenboom, Jacob P.; Kruit, Pieter

2014-06-01

Cathodoluminescence (CL) microscopy allows optical characterization of nanostructures at high spatial resolution. At the nanoscale, a main challenge of the technique is related to the background CL generated within the sample substrate. Here, we implement confocal detection of the CL signal to minimize the background contribution to the measurement. Nano-phosphors were used as point sources to evaluate the filtering capabilities of our confocal CL system, obtaining an axial intensity profile with 2.7 μm full width at half maximum for the central peak, in good correspondence with theoretical expectations. Considering the electron interaction volume, we found that the confocal filter becomes effective for electron energies above 20 keV, when using a 25 μm pinhole (0.86 Airy units). To illustrate our approach, we present confocal CL imaging of gold nanowires and triangular shaped plates deposited on an indium-tin oxide covered glass substrate, comparing the images with those obtained in standard unfiltered CL detection. The results show that confocal CL microscopy is a valuable tool for the investigation of nanostructures on highly cathodoluminescent substrates, widely used in biological and optical applications.

Simultaneous detection of iodine and iodide on boron doped diamond electrodes.

PubMed

Fierro, Stéphane; Comninellis, Christos; Einaga, Yasuaki

2013-01-15

Individual and simultaneous electrochemical detection of iodide and iodine has been performed via cyclic voltammetry on boron doped diamond (BDD) electrodes in a 1M NaClO(4) (pH 8) solution, representative of typical environmental water conditions. It is feasible to compute accurate calibration curve for both compounds using cyclic voltammetry measurements by determining the peak current intensities as a function of the concentration. A lower detection limit of about 20 μM was obtained for iodide and 10 μM for iodine. Based on the comparison between the peak current intensities reported during the oxidation of KI, it is probable that iodide (I(-)) is first oxidized in a single step to yield iodine (I(2)). The latter is further oxidized to obtain IO(3)(-). This technique, however, did not allow for a reasonably accurate detection of iodate (IO(3)(-)) on a BDD electrode. Copyright © 2012 Elsevier B.V. All rights reserved.

Two New Real-Time PCR-based Surveillance Systems for “Candidatus Liberibacter” Species Detection

USDA-ARS?s Scientific Manuscript database

We developed two novel surveillance systems for “Candidatus Liberibacter” (CL) species detection and identification. The first system is called “single tube dual primer Taq-Man PCR” (STDP). The procedure involves two sequential rounds of PCR using the CL asiaticus species-specific outer and inner pr...

The role of metasomatism in the balance of halogens in ore-forming process at porphyry Cu-Mo deposits

NASA Astrophysics Data System (ADS)

Berzina, A. N.

2009-04-01

Volatile components play an important role in the evolution of ore-magmatic systems and their ore potential. Of special interest are fluorine and chlorine compounds that principally control the transportation of ore elements by the fluid in a magmatic process and under high-temperature hydrothermal conditions. Study of the evolution of fluorine-chlorine activity in the ore-forming process and their source is usually based on analysis of their magmatic history, whereas the additional source of fluorine and chlorine released during metasomatic alteration of rocks hosting mineralization is poorly discussed in the existing literature. Based on microprobe data on Cl and F abundances in halogen-containing minerals (biotite, amphibole, apatite, titanite) in intrusive rocks and their hydrothermally altered varieties, the role of metasomatic processes in the balance of volatiles in the ore-forming system is discussed by the example of porphyry Cu-Mo deposits of Siberia (Russia) and Mongolia. Two groups of the deposits are considered: copper-molybdenum (Erdenetiin Ovoo, Mongolia and Aksug, Russia) with prevailing propylitic and phyllic alteration and molybdenum-copper (Sora, Russia), with predominant potassic alteration. All types of hydrothermal alterations have led to drastic decrease in Cl contents in metasomatic minerals as compared with halogen-containing magmatic minerals. All studied deposits (particularly those where propylitic and phyllic alteration were developed) show a nearly complete chlorine removal from altered halogen-containing rock-forming minerals (biotite and amphibole). The Cl content in amphibole decreases several times at the stage of replacement with actinolite in the process of propylitization. In the later chlorites (ripidolite and brunsvigite) that replace amphibole, actinolite, and biotite, chlorine is not detected by microprobe (detection limit 0.01-0.02% Cl). Chlorine was also not detected in white micas (muscovite-phengite series) in quartz-sericite alteration zones. No Cl-bearing minerals were revealed in ore-metasomatic assemblages with the exception of extremely low Cl contents in secondary biotite and very rare low-Cl apatite in the early potassic alteration zone. In contrast, fluorine concentrates in chlorites and white micas; however, the F content in them is commonly lower than in dark minerals, especially in biotite from altered rocks. The highest F contents are typical of biotites related to potassic alteration (K-feldspar + biotite + quartz assemblage). For example, the F content at the Sora deposit ranges from 2.5-2.7 wt.% in the metasomatic biotite to 0.44-1.63 wt.% in the rock-forming biotite of host granitoids. At this deposit, fluorite is a major mineral of the ore-metasomatic assemblage. The Mo-rich Sora deposit drastically differs from the Cu-rich Erdenetiin Ovoo and Aksug deposits by extremely low (0.02-0.08 wt.%) Cl contents in dark minerals from all of the host rocks. The considerable quantity of chlorine released as a result of large-scale propylitic and phyllic alteration from halogen-bearing dark minerals at Cu-rich deposits considerably affected the general Cl budget in the ore-metasomatic system. This could significantly promote the generation of Cl-rich (up to 50-70 wt.% NaCl-equiv.) ore-forming solutions at such deposits. At the Sora deposit characterized by less concentrated ore-bearing solutions (12-20 wt.% NaCl-equiv.), the metasomatic alteration of host rocks was not accompanied by an appreciable removal of Cl. At the studied deposits, huge volumes of enclosing rocks were involved in metasomatism. The large amounts of halogens released during the metasomatic alteration of host rocks might have significantly influenced the balance of volatiles in the ore forming system, including the increase in the salinity of hydrothermal solutions.

Application of hollow fiber liquid phase microextraction for simultaneous determination of regulated and emerging iodinated trihalomethanes in drinking water.

PubMed

Domínguez-Tello, A; Arias-Borrego, A; García-Barrera, T; Gómez-Ariza, J L

2015-07-10

Trihalomethanes (THMs) are regulated disinfection by-products (DBPs) most commonly analyzed in quality control water supply due to their harmful effects on health. However, few data exist about the content of emerging iodo-trihalomethanes (I-THMs) which are present in drinking water at very low concentrations (in the order of ngL(-1)). For this reason a two-phase hollow fiber liquid phase microextraction method for the simultaneous determination of four regulated trihalomethanes and six emerging iodo-trihalomethanes using GC-μECD and GC-MS with detection limits in the range of few ngL(-1) has been developed. A central composite design was used to optimize conditions for simultaneous extraction. The best extraction recovery was obtained with 19.2min at 27.1°C and 900rpm, without salt addition, using a supported hollow fiber membrane of 10.5cm (0.6mm id) and 1-octanol as acceptor phase. The limits of detection for the regulated THMs and I-THMs were 3-44ngL(-1) and 1-3ngL(-1), respectively. The calibration curves showed good linearity (R(2)>0.995) and good repeatibility (3-22%). The relative recoveries in water were between 96.5% and 105.2%. The method was applied for the simultaneous determination of trihalomethanes in supply water samples from seven water distribution systems (WDS) in the Huelva area, located at the southwest Spain, which use different water-treatment processes. The highest concentrations of I-THMs, particularly CHBrClI and CHCl2I, were detected in water treated with advanced treatment process using pre-ozonation, however these compounds were not detected or decreased along distribution system. In the samples of treated water with conventional treatment, using pre-oxidation by permanganate and distribution network, CHCl2I, CHBrClI, CHClI2, CHBrI2 and CHI3 were detected at very low concentrations (1-18ngL(-1)). Finally, in water samples from underground origin without oxidation treatment, in which only disinfection with sodium hypochlorite was applied, I-THMs were not detected. Copyright © 2015 Elsevier B.V. All rights reserved.

Concentration-dependence of the explosion characteristics of chlorine dioxide gas.

PubMed

Jin, Ri-ya; Hu, Shuang-qi; Zhang, Yin-ghao; Bo, Tao

2009-07-30

The explosion characteristics of chlorine dioxide gas have been studied for the first time in a cylindrical exploder with a shell capacity of 20 L. The experimental results have indicated that the lower concentration limit for the explosive decomposition of chlorine dioxide gas is 9.5% ([ClO(2)]/[air]), whereas there is no corresponding upper concentration limit. Under the experimental conditions, and within the explosion limits, the pressure of explosion increases with increasing concentration of chlorine dioxide gas; the maximum pressure of explosion relative to the initial pressure was measured as 0.024 MPa at 10% ClO(2) and 0.641 MPa at 90% ClO(2). The induction time (the time from the moment of sparking to explosion) has also been found to depend on the concentration of chlorine dioxide gas; thus, at 10% ClO(2) the induction time was 2195 ms, but at 90% ClO(2) the induction time was just 8 ms. The explosion reaction mechanism of ClO(2) is of a degenerate chain-branching type involving the formation of a stable intermediate (Cl(2)O(3)), from which the chain-branching occurs. Chain initiation takes place at the point of ignition and termination takes place at the inner walls of the exploder.

Trends in the Prevalence and Disparity in Cognitive Limitations of Americans 55-69 Years Old.

PubMed

Choi, HwaJung; Schoeni, Robert F; Martin, Linda G; Langa, Kenneth M

2018-04-16

To determine whether the prevalence of cognitive limitation (CL) among Americans ages 55 to 69 years changed between 1998 and 2014, and to assess the trends in socioeconomic disparities in CL among groups defined by race/ethnicity, education, income, and wealth. Logistic regression using 1998-2014 data from the biennial Health and Retirement Study, a nationally representative data set. CL is defined as a score of 0-11 on a 27-point cognitive battery of items focused on memory. Socioeconomic status (SES) measures are classified as quartiles. In models controlling for age, gender, and previous cognitive testing, we find no significant change over time in the overall prevalence of CL, widening disparities in limitation by income and, in some cases, wealth, and improvements among non-Hispanic whites but not other racial/ethnic groups. Among people 55-69, rates of CL are many times higher for groups with lower SES than those with higher SES, and recent trends show little indication that the gaps are narrowing.

X-ray detection capability of a BaCl{sub 2} single crystal scintillator

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koshimizu, Masanori; CREST, Japan Science and Technology Agency, Sanbancho, Chiyoda-ku, Tokyo 102-0075; Onodera, Kazuya

2012-01-15

The x-ray detection capability of a scintillation detector equipped with a BaCl{sub 2} single crystal was evaluated. The scintillation decay kinetics can be expressed by a sum of two exponential decay components. The fast and slow components have lifetimes of 1.5 and 85 ns, respectively. The total light output is 5% that of YAP:Ce. A subnanosecond timing resolution was obtained. The detection efficiency of a 67.41 keV x-ray is 87% for a detector equipped with a BaCl{sub 2} crystal 6-mm thick. Thus, excellent timing resolution and high detection efficiency can be simultaneously achieved. Additionally, luminescence decay characteristics under vacuum ultravioletmore » excitation have been investigated. Radiative decay of self-trapped excitons is thought to be responsible for the fast scintillation component.« less

Dynamic potential and surface morphology study of sertraline membrane sensors

PubMed Central

Khater, M.M.; Issa, Y.M.; Hassib, H.B.; Mohammed, S.H.

2014-01-01

New rapid, sensitive and simple electrometric method was developed to determine sertraline hydrochloride (Ser-Cl) in its pure raw material and pharmaceutical formulations. Membrane sensors based on heteropolyacids as ion associating material were prepared. Silicomolybdic acid (SMA), silicotungstic acid (STA) and phosphomolybdic acid (PMA) were used. The slope and limit of detection are 50.00, 60.00 and 53.24 mV/decade and 2.51, 5.62 and 4.85 μmol L−1 for Ser-ST, Ser-PM and Ser-SM membrane sensors, respectively. Linear range is 0.01–10.00 for the three sensors. These new sensors were used for the potentiometric titration of Ser-Cl using sodium tetraphenylborate as titrant. The surface morphologies of the prepared membranes with and without the modifier (ion-associate) were studied using scanning and atomic force microscopes. PMID:26257944

Co-metal-organic-frameworks with pure uniform crystal morphology prepared via Co2 + exchange-mediated transformation from Zn-metallogels for luminol catalysed chemiluminescence

NASA Astrophysics Data System (ADS)

Tang, Xue Qian; Xiao, Bo Wen; Li, Chun Mei; Wang, Dong Mei; Huang, Cheng Zhi; Li, Yuan Fang

2017-03-01

Cation exchange-mediated transformation from Zn-metallogels (MOGs), which was a mild facile strategy relative to the demanding hydrothermal method, was employed to develop Co2 + metal-organic frameworks (Co-MOFs) at room temperature. The obtained Co-MOFs was of uniform octahedral morphology and possessed high activity to catalyze luminol chemiluminescence without extra oxidants. By adding cysteine, the CL emission of luminol-Co-MOFs system was further enhanced. Based on this phenomenon, Co-MOFs was utilized to build a practical sensing platform for cysteine determination. Under the optimized conditions, the relative CL intensity (ΔI) was proportional to the concentration of cysteine in the range of 2-10 μM, and the detection limit was 0.49 μM (3S/N). Moreover, the established method was applied to the determination of cysteine in commercially available pharmaceutical injections.

The nongravitational interactions of dark matter in colliding galaxy clusters.

PubMed

Harvey, David; Massey, Richard; Kitching, Thomas; Taylor, Andy; Tittley, Eric

2015-03-27

Collisions between galaxy clusters provide a test of the nongravitational forces acting on dark matter. Dark matter's lack of deceleration in the "bullet cluster" collision constrained its self-interaction cross section σ(DM)/m < 1.25 square centimeters per gram (cm(2)/g) [68% confidence limit (CL)] (σ(DM), self-interaction cross section; m, unit mass of dark matter) for long-ranged forces. Using the Chandra and Hubble Space Telescopes, we have now observed 72 collisions, including both major and minor mergers. Combining these measurements statistically, we detect the existence of dark mass at 7.6σ significance. The position of the dark mass has remained closely aligned within 5.8 ± 8.2 kiloparsecs of associated stars, implying a self-interaction cross section σ(DM)/m < 0.47 cm(2)/g (95% CL) and disfavoring some proposed extensions to the standard model. Copyright © 2015, American Association for the Advancement of Science.

Study of atomic and molecular emission spectra of Sr by laser induced breakdown spectroscopy (LIBS).

PubMed

Bhatt, Chet R; Alfarraj, Bader; Ayyalasomayajula, Krishna K; Ghany, Charles; Yueh, Fang Y; Singh, Jagdish P

2015-12-01

Laser Induced Breakdown Spectroscopy (LIBS) is an ideal analytical technique for in situ analysis of elemental composition. We have performed a comparative study of the quantitative and qualitative analysis of atomic and molecular emission from LIBS spectra. In our experiments, a mixture of SrCl2 and Al2O3 in powder form was used as a sample. The atomic emission from Sr and molecular emission from SrCl and SrO observed in LIBS spectra were analyzed. The optimum laser energies, gate delays, and gate widths for selected atomic lines and molecular bands were determined from spectra recorded at various experimental parameters. These optimum experimental conditions were used to collect calibration data, and the calibration curves were used to predict the Sr concentration. Limits of detection (LODs) for selected atomic and molecular emission spectra were determined.

Hollow Cathode Plasma-Enhanced Atomic Layer Deposition of Silicon Nitride Using Pentachlorodisilane.

PubMed

Meng, Xin; Kim, Harrison Sejoon; Lucero, Antonio T; Hwang, Su Min; Lee, Joy S; Byun, Young-Chul; Kim, Jiyoung; Hwang, Byung Keun; Zhou, Xiaobing; Young, Jeanette; Telgenhoff, Michael

2018-04-25

In this work, a novel chlorodisilane precursor, pentachlorodisilane (PCDS, HSi 2 Cl 5 ), was investigated for the growth of silicon nitride (SiN x ) via hollow cathode plasma-enhanced atomic layer deposition (PEALD). A well-defined self-limiting growth behavior was successfully demonstrated over the growth temperature range of 270-360 °C. At identical process conditions, PCDS not only demonstrated approximately >20% higher growth per cycle than that of a commercially available chlorodisilane precursor, hexachlorodisilane (Si 2 Cl 6 ), but also delivered a better or at least comparable film quality determined by characterizing the refractive index, wet etch rate, and density of the films. The composition of the SiN x films grown at 360 °C using PCDS, as determined by X-ray photoelectron spectroscopy, showed low O content (∼2 at. %) and Cl content (<1 at. %; below the detection limit). Fourier transform infrared spectroscopy spectra suggested that N-H bonds were the dominant hydrogen-containing bonds in the SiN x films without a significant amount of Si-H bonds originating from the precursor molecules. The possible surface reaction pathways of the PEALD SiN x using PCDS on the surface terminated with amine groups (-NH 2 and -NH-) are proposed. The PEALD SiN x films grown using PCDS also exhibited a leakage current density as low as 1-2 nA/cm 2 at 2 MV/cm and a breakdown electric field as high as ∼12 MV/cm.

Cytoskeletal confinement of CX3CL1 limits its susceptibility to proteolytic cleavage by ADAM10

PubMed Central

Wong, Harikesh S.; Jaumouillé, Valentin; Heit, Bryan; Doodnauth, Sasha A.; Patel, Sajedabanu; Huang, Yi-Wei; Grinstein, Sergio; Robinson, Lisa A.

2014-01-01

CX3CL1 is a unique chemokine that acts both as a transmembrane endothelial adhesion molecule and, upon proteolytic cleavage, a soluble chemoattractant for circulating leukocytes. The constitutive release of soluble CX3CL1 requires the interaction of its transmembrane species with the integral membrane metalloprotease ADAM10, yet the mechanisms governing this process remain elusive. Using single-particle tracking and subdiffraction imaging, we studied how ADAM10 interacts with CX3CL1. We observed that the majority of cell surface CX3CL1 diffused within restricted confinement regions structured by the cortical actin cytoskeleton. These confinement regions sequestered CX3CL1 from ADAM10, precluding their association. Disruption of the actin cytoskeleton reduced CX3CL1 confinement and increased CX3CL1–ADAM10 interactions, promoting the release of soluble chemokine. Our results demonstrate a novel role for the cytoskeleton in limiting membrane protein proteolysis, thereby regulating both cell surface levels and the release of soluble ligand. PMID:25253723

Multilayers enzyme-coated carbon nanotubes as biolabel for ultrasensitive chemiluminescence immunoassay of cancer biomarker.

PubMed

Bi, Sai; Zhou, Hong; Zhang, Shusheng

2009-06-15

A novel and ultrasensitive chemiluminescence immunoassay (CLIA) method based on multiple enzyme layers assembled multiwall carbon nanotubes (MWCNTs) as signal amplification labels was developed by employing luminol-H(2)O(2)-HRP-bromophenol blue (BPB) enhanced chemiluminescence (CL) system for the detection of a cancer biomarker in human serum samples, as exemplified by the measurement of alpha-fetoprotein (AFP) as a model protein. In this study, horseradish peroxidase (HRP) was assembled onto MWCNTs templates layer-by-layer (LBL) through electrostatic interactions with polyion PDDA, and further conjugated with AFP secondary antibodies (Ab(2)) as the enzyme label. The resulting LBL assembly could maximize the ratio of HRP/Ab(2) which could amplify the sensitivity greatly. To the best of our knowledge, it was the first time for this strategy applied in CLIA to date. Under the optimum conditions of luminol-H(2)O(2)-HRP-BPB CL system and the sandwich immunoreactions, a linear range from 0.02 to 2.0 ng/mL (R=0.9980) was obtained with the detection limit of 8.0 pg/mL (3sigma) which was two orders of magnitude lower than standard ELISA method. Furthermore, accurate detection of AFP in human serum samples was also demonstrated by comparison to ELISA assays. From the above results, such signal amplification strategy proposed by the novel CNT-LBL enzyme label showed an excellent promise for ultrasensitive detection of cancer biomarkers in clinical laboratory.

An enhanced chemiluminescence resonance energy transfer system based on target recycling G-guadruplexes/hemin DNAzyme catalysis and its application in ultrasensitive detection of DNA.

PubMed

Chen, Jia; Huang, Yong; Vdovenko, Marina; Sakharov, Ivan Yu; Su, Guifa; Zhao, Shulin

2015-06-01

An enhanced chemiluminescence resonance energy transfer (CRET) system based on target recycling G-guadruplexes/hemin DNAzyme catalysis was developed for ultrasensitive detection of DNA. CRET system consists of luminol as chemiluminescent donor, and fluorescein isothiocyanate (FITC) as acceptor. The sensitive detection was achieved by using the system consisted of G-riched DNA, blocker DNA, and the Nb.BbvCI biocatalyst. Upon addition of target DNA to the system, target DNA hybridizes with the quasi-circular DNA structure, and forms a DNA duplex. The formation of DNA duplex triggers selective enzymatic cleavage of quasi-circular DNA by Nb.BbvCI, resulting in the release of target DNA and two G-riched DNAzyme segments. Released target DNA then hybridizes with another quasi-circular DNA structure to initiate the cleavage of the quasi-circular DNA structure. Eventually, each target DNA can go through many cycles, resulting in the digestion of many quasi-circular DNA structures, generating many G-riched DNAzyme segments. G-riched DNAzyme segment products assemble with hemin to form stable hemin/G-quadruplexes that exhibit peroxidase-like activity which can catalyze the oxidation of luminol by H2O2 to produce CL signals. In the presence of FITC, CL of luminol can excite FITC molecules, and thus produced CRET between the luminol and FITC. This unique analysis strategy gives a detection limit down to 80 fM, which is at least four orders of magnitude lower than that of unamplified DNA detection methods. Copyright © 2015 Elsevier B.V. All rights reserved.

The aluminum electrode in AlCl3-alkali-halide melts.

NASA Technical Reports Server (NTRS)

Holleck, G. L.; Giner, J.

1972-01-01

Passivation phenomena have been observed upon cathodic and anodic polarization of the Al electrode in AlCl3-KCl-NaCl melts between 100 and 160 C. They are caused by formation of a solid salt layer at the electrode surface resulting from concentration changes upon current flow. The anodic limiting currents increased with temperature and with decreasing AlCl3 content of the melt. Current voltage curves obtained on a rotating aluminum disk showed a linear relationship between the anodic limiting current and omega to the minus 1/2 power. Upon cathodic polarization, dendrite formation occurs at the Al electrode. The activation overvoltage in AlCl3-KCl-NaCl was determined by galvanostatic current step methods. An apparent exchange current density of 270 mA/sq cm at 130 C and a double layer capacity of 40 plus or minus 10 microfarad/sq cm were measured.

Multiway analysis applied to time-resolved chemiluminescence for simultaneous determination of paracetamol and codeine in pharmaceuticals.

PubMed

Mokhtari, Ali; Jafari Delouei, Nastaran; Keyvanfard, Mohsen; Abdolhosseini, Mohammad

2016-09-01

This method is based on the enhancing effect of codeine (COD) and paracetamol (PAR) on the chemiluminescence (CL) reaction of Ru(phen)3 (2+) with Ce(IV). In the batch mode, COD gives a relatively sharp peak with the highest CL intensity at 4.0 s, whereas the maximum CL intensity of the PAR appears at ~60 s after injection of Ce(IV) solution. Whole CL time profiles allowed use of the time-resolved CL data in combination with multiway calibration techniques, as multiway partial least squares (N-PLS), for the quantitative determination of both COD and PAR in binary mixtures. In this work, we found that the impact of Ce(IV) concentration on the CL intensity was different for COD and PAR. Therefore, a Ce(IV) concentration mode was added to the time and sample modes to obtain 3D data. The percent relative standard deviation (%RSD) values for 10 determinations of 1.0 × 10(-5)  mol/L of COD and 1.0 × 10(-4)  mol/L of PAR were 6.1% and 8.7%, respectively. The limit of detection (LOD) values (S/N = 3) were 0.9 × 10(-8)  mol/L and 1.0 × 10(-6)  mol/L for COD and PAR, respectively. The proposed method was successfully applied to the determination of PAR and COD in commercial pharmaceutical formulations. Acceptable recoveries (90-110%) were obtained for the quantification of these drugs in the real samples. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Solar photocatalytic disinfection of E. coli and bacteriophages MS2, ΦX174 and PR772 using TiO2, ZnO and ruthenium based complexes in a continuous flow system.

PubMed

Mac Mahon, Joanne; Pillai, Suresh C; Kelly, John M; Gill, Laurence W

2017-05-01

The performance of photocatalytic treatment processes were assessed using different photocatalysts against E. coli and bacteriophages MS2, ΦX174 and PR772, in a recirculating continuous flow compound parabolic collector system under real sunlight conditions. Suspended TiO 2 and ZnO nanoparticle powders and Tris(2,2'-bipyridyl)dichlororuthenium(II) hexahydrate in solution were tested separately, as well as in combination, using E. coli. For a 3-log reduction of E. coli in distilled water, inactivation rates in terms of cumulative dose were in the order Ru(bpy) 3 Cl 2 >(TiO 2 & Ru(bpy) 3 Cl 2 )>(ZnO & Ru(bpy) 3 Cl 2 )>ZnO>TiO 2 >photolysis. Reactivation of E. coli was observed following all trials despite the detection limit being reached, although the reactivated colonies were observed to be under stress and much slower growing when compared to original colonies. Treatment with Ru(bpy) 3 Cl 2 was also compared against standard photolysis of bacteriophages MS2, ΦX174 and PR772 with the order of photolytic inactivation for a 3-log reduction in terms of cumulative UV-A dose being ΦX174>PR772>MS2. However, MS2 was found to be the most susceptible bacteriophage to treatment with Ru(bpy) 3 Cl 2 , with complete removal of the phage observed within the first 15min of exposure. Ru(bpy) 3 Cl 2 also significantly improved inactivation rates for PR772 and ΦX174. Copyright © 2017 Elsevier B.V. All rights reserved.

Pharmacokinetic of pseudoephedrine in rat serum with luminol-pepsin chemiluminescence system by flow injection analysis.

PubMed

Luo, Kai; Li, Yajuan; Zheng, Xiaohui; Song, Zhenghua

2015-02-01

Pepsin (Pep) accelerated the electron transferring rate of excited 3-aminophathlate and enhanced luminol-dissolved oxygen chemiluminescence (CL) intensity, and the flow injection (FI) luminol-Pep CL system was first developed. It was found that the CL intensity of luminol-Pep reaction could be remarkably inhibited by pseudoephedrine (PE); the decrement of CL intensity was linear to the logarithm of PE concentration in the range of 0.1∼100.0 nmol L(-1) with a detection limit of 0.03 nmol mL(-1) (3σ). At a flow rate of 2.0 mL min(-1), the complete process including washing and sampling was performed within 40 s, offering a sample throughput of 90 h(-1). This proposed method was successfully applied to determining PE in rat serum for 18 h after intragastric administration with the elimination ratio of 42.34 % and recoveries from 90.3 to 110.6 %. The pharmacokinetic results showed that PE could be rapidly absorbed into serum with peak concentration (C max) of 1.45 ± 0.18 g L(-1) at the time (T max) of 1.49 ± 0.02 h; the absorption half-life (0.35 ± 0.04 h), elimination half-life (1.86 ± 0.24 h), the area under curve (109.81 ± 6.03 mg L(-1) h(-1)), mean residence time (3.82 ± 0.27 h), and elimination rate constant (2.26 ± 0.23 L g(-1) h(-1)) in rats vivo were derived, respectively. The possible CL mechanism of luminol-Pep-PE reaction was discussed by FI-CL, fluorescence, and molecular docking (MD) methods.

Cathodoluminescence in the scanning transmission electron microscope.

PubMed

Kociak, M; Zagonel, L F

2017-05-01

Cathodoluminescence (CL) is a powerful tool for the investigation of optical properties of materials. In recent years, its combination with scanning transmission electron microscopy (STEM) has demonstrated great success in unveiling new physics in the field of plasmonics and quantum emitters. Most of these results were not imaginable even twenty years ago, due to conceptual and technical limitations. The purpose of this review is to present the recent advances that broke these limitations, and the new possibilities offered by the modern STEM-CL technique. We first introduce the different STEM-CL operating modes and the technical specificities in STEM-CL instrumentation. Two main classes of optical excitations, namely the coherent one (typically plasmons) and the incoherent one (typically light emission from quantum emitters) are investigated with STEM-CL. For these two main classes, we describe both the physics of light production under electron beam irradiation and the physical basis for interpreting STEM-CL experiments. We then compare STEM-CL with its better known sister techniques: scanning electron microscope CL, photoluminescence, and electron energy-loss spectroscopy. We finish by comprehensively reviewing recent STEM-CL applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Cathodoluminescence in the scanning transmission electron microscope.

PubMed

Kociak, M; Zagonel, L F

2016-12-19

Cathodoluminescence (CL) is a powerful tool for the investigation of optical properties of materials. In recent years, its combination with scanning transmission electron microscopy (STEM) has demonstrated great success in unveiling new physics in the field of plasmonics and quantum emitters. Most of these results were not imaginable even twenty years ago, due to conceptual and technical limitations. The purpose of this review is to present the recent advances that broke these limitations, and the new possibilities offered by the modern STEM-CL technique. We first introduce the different STEM-CL operating modes and the technical specificities in STEM-CL instrumentation. Two main classes of optical excitations, namely the coherent one (typically plasmons) and the incoherent one (typically light emission from quantum emitters) are investigated with STEM-CL. For these two main classes, we describe both the physics of light production under electron beam irradiation and the physical basis for interpreting STEM-CL experiments. We then compare STEM-CL with its better known sister techniques: scanning electron microscope CL, photoluminescence, and electron energy-loss spectroscopy. We finish by comprehensively reviewing recent STEM-CL applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Nucleic acid sensor for insecticide detection.

PubMed

Solanki, Pratima R; Prabhakar, Nirmal; Pandey, M K; Malhotra, B D

2008-01-01

Nucleic acid sensor based on polyaniline (PANI) has been fabricated by covalently immobilizing double stranded calf thymus (dsCT) DNA onto perchlorate (ClO(-) (4))-doped PANI film deposited onto indium-tin-oxide (ITO) glass plate using 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC)/N-hydroxysuccinimide (NHS) chemistry. These dsCT-DNA-PANI-ClO(4)/ITO and PANI-ClO(4)/ITO electrodes have been characterized using square wave voltammetry, electrochemical impedance, scanning electron microscopy (SEM) and Fourier-transform-infrared (FTIR) measurements. This disposable dsCT-DNA-PANI-ClO(4)/ITO bioelectrode, stable for about 4 months, can be used to detect cypermethrin (0.005 ppm) and trichlorfon (0.01 ppm) in 30 and 60 s, respectively. John Wiley & Sons, Ltd

Monitoring of Legionella pneumophila viability after chlorine dioxide treatment using flow cytometry.

PubMed

Mustapha, Pascale; Epalle, Thibaut; Allegra, Séverine; Girardot, Françoise; Garraud, Olivier; Riffard, Serge

2015-04-01

The viability of three Legionella pneumophila strains was monitored after chlorine dioxide (ClO2) treatment using a flow cytometric assay. Suspensions of L. pneumophila cells were submitted to increasing concentrations of ClO2. Culturable cells were still detected when using 4 mg/L, but could no longer be detected after exposure to 6 mg/L of ClO2, although viable but not culturable (VBNC) cells were found after exposure to 4-5 mg/L of ClO2. When testing whether these VBNC were infective, two of the strains were resuscitated after co-culture with Acanthamoeba polyphaga, but neither of them could infect macrophage-like cells. Copyright © 2015 Institut Pasteur. Published by Elsevier Masson SAS. All rights reserved.

The infrared spectral analysis of CF/sub 2Cl/sub 2

NASA Technical Reports Server (NTRS)

1984-01-01

The CF2Cl2 absorption bands at 1/923 cm and 1/1161 cm are examined as to their detectability in long-path solar spectroscopy. Measurements are reported for a long-path White Cell. A cryo-condensation unit was also constructed to test its ability to improve detection of trace gases in the ambient atmosphere.

Chemiluminescence generation and detection in a capillary-driven microfluidic chip

NASA Astrophysics Data System (ADS)

Ramon, Charlotte; Temiz, Yuksel; Delamarche, Emmanuel

2017-02-01

The use of microfluidic technology represents a strong opportunity for providing sensitive, low-cost and rapid diagnosis at the point-of-care and such a technology might therefore support better, faster and more efficient diagnosis and treatment of patients at home and in healthcare settings both in developed and developing countries. In this work, we consider luminescence-based assays as an alternative to well-established fluorescence-based systems because luminescence does not require a light source or expensive optical components and is therefore a promising detection method for point-of-care applications. Here, we show a proof-of-concept of chemiluminescence (CL) generation and detection in a capillary-driven microfluidic chip for potential immunoassay applications. We employed a commercial acridan-based reaction, which is catalyzed by horseradish peroxidase (HRP). We investigated CL generation under flow conditions using a simplified immunoassay model where HRP is used instead of the complete sandwich immunocomplex. First, CL signals were generated in a capillary microfluidic chip by immobilizing HRP on a polydimethylsiloxane (PDMS) sealing layer using stencil deposition and flowing CL substrate through the hydrophilic channels. CL signals were detected using a compact (only 5×5×2.5 cm3) and custom-designed scanner, which was assembled for less than $30 and comprised a 128×1 photodiode array, a mini stepper motor, an Arduino microcontroller, and a 3D-printed housing. In addition, microfluidic chips having specific 30-μm-deep structures were fabricated and used to immobilize ensembles of 4.50 μm beads functionalized with HRP so as to generate high CL signals from capillary-driven chips.

Amperometric determination of nitrite using natural fibers as template for titanium dioxide nanotubes with immobilized hemin as electron transfer mediator.

PubMed

Ranjani, Balasubramanian; Kalaiyarasi, Jayaprakasham; Pavithra, Loganathan; Devasena, Thiyagarajan; Pandian, Kannaiyan; Gopinath, Subash C B

2018-02-23

A sensing device was constructed for the amperometric determination of nitrite. It is based on the use of titanium dioxide (TiO 2 ) nanotubes template with natural fibers and carrying hemin acting as the electron mediator. A glassy carbon electrode (GCE) was modified with the hemin/TNT nanocomposite. The electrochemical response to nitrite was characterized by impedance spectroscopy and cyclic voltammetry. An amperometric study, performed at a working potential of + 0.75 V (vs. Ag/AgCl), showed the sensor to enable determination of nitrite with a linear response in the 0.6 to 130 μM concentration range and with a 59 nM limit of detection. Corresponding studies by differential study voltammetry (E p  = 0.75 V) exhibited a linear range from 0.6 × 10 -6 to 7.3 × 10 -5  M with a limit of detection of 84 nM. The sensing device was applied to the determination of nitrite in spiked tap and lake water samples. Graphical abstract Natural fibers templated synthesis of TNT immobilized hemin as electron transfer mediator for quantitative detection of nitrite with detection limit of 59 nM and good electrochemical sensitivity and the method can be used for quantitative determination of nitrite in water samples.

Paper-Based Electrochemical Detection of Chlorate

PubMed Central

Shriver-Lake, Lisa C.; Zabetakis, Dan; Dressick, Walter J.; Stenger, David A.; Trammell, Scott A.

2018-01-01

We describe the use of a paper-based probe impregnated with a vanadium-containing polyoxometalate anion, [PMo11VO40]5−, on screen-printed carbon electrodes for the electrochemical determination of chlorate. Cyclic voltammetry (CV) and chronocoulometry were used to characterize the ClO3− response in a pH = 2.5 solution of 100 mM sodium acetate. A linear CV current response was observed between 0.156 and 1.25 mg/mL with a detection limit of 0.083 mg/mL (S/N > 3). This performance was reproducible using [PMo11VO40]5−-impregnated filter paper stored under ambient conditions for as long as 8 months prior to use. At high concentration of chlorate, an additional catalytic cathodic peak was seen in the reverse scan of the CVs, which was digitally simulated using a simple model. For chronocoulometry, the charge measured after 5 min gave a linear response from 0.625 to 2.5 mg/mL with a detection limit of 0.31 mg/mL (S/N > 3). In addition, the slope of charge vs. time also gave a linear response. In this case the linear range was from 0.312 to 2.5 mg/mL with a detection limit of 0.15 mg/mL (S/N > 3). Simple assays were conducted using three types of soil, and recovery measurements reported. PMID:29364153

Near-infrared spectroscopy for the detection and quantification of bacterial contaminations in pharmaceutical products.

PubMed

Quintelas, Cristina; Mesquita, Daniela P; Lopes, João A; Ferreira, Eugénio C; Sousa, Clara

2015-08-15

Accurate detection and quantification of microbiological contaminations remains an issue mainly due the lack of rapid and precise analytical techniques. Standard methods are expensive and time-consuming being associated to high economic losses and public health threats. In the context of pharmaceutical industry, the development of fast analytical techniques able to overcome these limitations is crucial and spectroscopic techniques might constitute a reliable alternative. In this work we proved the ability of Fourier transform near infrared spectroscopy (FT-NIRS) to detect and quantify bacteria (Bacillus subtilis, Escherichia coli, Pseudomonas fluorescens, Salmonella enterica, Staphylococcus epidermidis) from 10 to 10(8) CFUs/mL in sterile saline solutions (NaCl 0.9%). Partial least squares discriminant analysis (PLSDA) models showed that FT-NIRS was able to discriminate between sterile and contaminated solutions for all bacteria as well as to identify the contaminant bacteria. Partial least squares (PLS) models allowed bacterial quantification with limits of detection ranging from 5.1 to 9 CFU/mL for E. coli and B. subtilis, respectively. This methodology was successfully validated in three pharmaceutical preparations (contact lens solution, cough syrup and topic anti-inflammatory solution) proving that this technique possess a high potential to be routinely used for the detection and quantification of bacterial contaminations. Copyright © 2015 Elsevier B.V. All rights reserved.

The Investigation of Chlorates as a Possible Source of Oxygen and Chlorine Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Sutter, B.; Archer, D. P.; Ming, D. W.; Niles, P. B.; Eigenbrode, J. L.; Franz, H.; Glavin, D. P.; McAdam, A. C.; Mahaffy, P; Stern, J. C.;

Highly sensitive chemiluminescence immunoassay on chitosan membrane modified paper platform using TiO2 nanoparticles/multiwalled carbon nanotubes as label.

PubMed

Li, Weiping; Ge, Shenguang; Wang, Shoumei; Yan, Mei; Ge, Lei; Yu, Jinghua

2013-01-01

A highly sensitive chemiluminescence (CL) immunoassay was incorporated into a low-cost microfluidic paper-based analytical device (μ-PAD) to fabricate a facile paper-based CL immunodevice (denoted as μ-PCLI). This μ-PCLI was constructed by covalently immobilizing capture antibody on a chitosan membrane modified μ-PADs, which was developed by simple wax printing methodology. TiO2 nanoparticles coated multiwalled carbon nanotubes (TiO2/MWCNTs) were synthesized as an amplification catalyst tag to label signal antibody (Ab2). After sandwich-type immunoreactions, the TiO2/MWCNTs were captured on the surface of μ-PADs to catalyze the luminol-p-iodophenol-H2O2 CL system, which produced an enhanced CL emission. Using prostate-specific antigen as a model analyte, the approach provided a good linear response range from 0.001 to 20 ng/mL with a low detection limit of 0.8 pg/mL under optimal conditions. This μ-PCLI showed good reproducibility, selectivity and stability. The assay results of prostate-specific antigen in clinical serum samples were in good agreement with that obtained by commercially used electrochemiluminescence methods at the Cancer Research Center of Shandong Tumor Hospital (Jinan, Shandong Province, China). This μ-PCLI could be very useful to realize highly sensitive, qualitative point-of-care testing in developing or developed countries. Copyright © 2013 John Wiley & Sons, Ltd.

Oxalyl chloride, ClC(O)C(O)Cl: UV/vis spectrum and Cl atom photolysis quantum yields at 193, 248, and 351 nm.

PubMed

Ghosh, Buddhadeb; Papanastasiou, Dimitrios K; Burkholder, James B

2012-10-28

Oxalyl chloride, (ClCO)(2), has been used as a Cl atom photolytic precursor in numerous laboratory kinetic and photochemical studies. In this study, the UV/vis absorption spectrum of (ClCO)(2) and the Cl atom quantum yields in its photolysis at 193, 248, and 351 nm are reported. The UV∕vis spectrum was measured between 200 and 450 nm at 296 K using diode array spectroscopy in conjunction with an absolute cross section obtained at 213.9 nm. Our results are in agreement with the spectrum reported by Baklanov and Krasnoperov [J. Phys. Chem. A 105, 97-103 (2001)], which was obtained at 11 discrete wavelengths between 193.3 and 390 nm. Cl atom quantum yields, Φ(λ), were measured using pulsed laser photolysis coupled with time resolved atomic resonance fluorescence detection of Cl. The UV photolysis of (ClCO)(2) has been shown in previous studies to occur via an impulsive three-body dissociation mechanism, (COCl)(2) + hv → ClCO* + Cl + CO (2), where the excited ClCO radical, ClCO*, either dissociates or stabilizes ClCO* → Cl + CO (3a), → ClCO (3b). ClCO is thermally unstable at the temperatures (253-298 K) and total pressures (13-128 Torr) used in our experiments ClCO + M → Cl + CO + M (4) leading to the formation of a secondary Cl atom that was resolvable in the Cl atom temporal profiles obtained in the 248 and 351 nm photolysis of (ClCO)(2). Φ(193 nm) was found to be 2.07 ± 0.37 independent of bath gas pressure (25.8-105.7 Torr, N(2)), i.e., the branching ratio for channel 2a or the direct formation of 2Cl + 2CO in the photolysis of (ClCO)(2) is >0.95. At 248 nm, the branching ratio for channel 2a was determined to be 0.79 ± 0.15, while the total Cl atom yield, i.e., following the completion of reaction (4), was found to be 1.98 ± 0.26 independent of bath gas pressure (15-70 Torr, N(2)). Φ(351 nm) was found to be pressure dependent between 7.8 and 122.4 Torr (He, N(2)). The low-pressure limit of the total Cl atom quantum yield, Φ(0)(351 nm), was 2.05 ± 0.24. As part of this work, rate coefficients for the thermal decomposition of ClCO were measured between 253 and 298 K at total pressures between 13 and 128 Torr (He and N(2) bath gases). The N(2) bath gas results were combined with the data reported in Nicovich et al. [J. Chem. Phys. 92, 3539-3544 (1990)] to yield k(4)(T, N(2)) = (4.7 ± 0.7) × 10(-10) exp [-(2987 ± 16)/T] cm(3) molecule(-1) s(-1), while the He bath gas data fit yielded k(4)(T, He) = (2.3 ± 2.1) × 10(-10) exp [-(2886 ± 218)/T] cm(3) molecule(-1) s(-1). The quoted uncertainties are at the 2σ level from the precision of the fit. In addition, the room temperature rate coefficient for the Cl + ClNO reaction was measured in this work to be (1.03 ± 0.10) × 10(-10) cm(3) molecule(-1) s(-1).

High-sensitivity imaging method of singlet oxygen and superoxide anion in photodynamic and sonodynamic actions

NASA Astrophysics Data System (ADS)

Xing, Da; He, Yonghong; Hao, Min; Chen, Qun

2004-07-01

A novel method of photodynamic diagnosis (PDD) of cancer mediated by chemiluminescence (CL) probe is presented. The mechanism for photodynamic therapy (PDT) involves reactive oxygen species (ROS), such as singlet oxygen (1O2) and superoxide (O2-), generated by during the photochemical process. Both 1O2 and O2- can react with Cypridina luciferin analogue (FCLA), a highly selective CL probe for detecting the ROS. Chemiluminescence from the reaction of FCLA with the ROS, at about 530 nm, was detected by a highly sensitive ICCD system. The CL was markedly inhibited by the addition of 10 mmol/L sodium azide (NaN3) in a sample solution. Similar phenomena, with lesser extents of changes, were observed at the additions of 10 μmol/L superoxide dismutase (SOD), 10 mmol/L mannitol, and 100 μg/mL catalase, respectively. This indicates that the detected CL signals were mainly from ROS generated during the photosensitization reactions. Also, the chemiluminescence method was used to detect the ROS during sonodynamic action, both in vitro and in vivo. ROS formation during sonosensitizations of HpD and ATX-70 were detected using our newly-developed imaging technique, in real time, on tumor bearing animals. This method can provide a new means in clinics for tumor diagnosis.

Discovery of 21 New Changing-look AGNs: Study on Evolution of AGNs and AGN Host Galaxies

NASA Astrophysics Data System (ADS)

Yang, Qian; Wu, Xuebing; Fan, Xiaohui; Jiang, Linhua; McGreer, Ian; Shangguan, Jinyi; Yao, Su; Wang, Bingquan; Joshi, Ravi; Green, Richard F.; Wang, Feige; Feng, Xiaotong; Fu, Yuming; Yang, Jinyi; Liu, Yuanqi

2018-01-01

The rare case of changing-look (CL) AGNs, with the appearance or disappearance of broad Balmer emission lines within a few years, challenges our understanding of the AGN unified model. We present a sample of 21 new CL AGNs at 0.08 < z < 0.58. The new sample doubles the number of such objects known to date. These new CL AGNs were discovered by several ways, from repeat spectra in the SDSS, repeat spectra in the Large Sky Area Multi-Object Fiber Spectroscopic Telescope (LAMOST) and SDSS, and from photometric variability and new spectroscopic observations. The estimated upper limits of transition timescale of the CL AGNs in this sample span from 0.9 to 13 years in rest-frame. The continuum flux in the optical and mid-infrared becomes brighter when the CL AGNs turn on, or vice versa. Variations of more than 0.2 mag in the mid-infrared W1 band, from the Wide-field Infrared Survey Explorer (WISE), were detected in 15 CL AGNs during the transition. The optical and mid-infrared variability is not consistent with the scenario of variable obscuration in 10 CL AGNs at higher than 3σ confidence level. We confirm a bluer-when-brighter trend in the optical. However, the mid-infrared colors W1‑W2 become redder when the objects become brighter in the W1 band, possibly due to a stronger hot dust contribution in the W2 band when the AGN activity becomes stronger. The physical mechanism of type transition is important for understanding the evolution of AGNs. The rare CL AGNs provide exceptional cases for the black hole and host stellar velocity dispersion relation studies at higher redshift. The faint state spectrum can be used to obtain the host stellar velocity dispersion without contamination from AGN component, and the bright state spectrum can be used to calculate the black hole mass with broad Balmer emission lines. The images at the non-AGN phase of CL AGNs are useful for studies of AGN host galaxies avoiding contamination from the luminous central engines.

Measurements of scene spectral radiance variability

NASA Astrophysics Data System (ADS)

Seeley, Juliette A.; Wack, Edward C.; Mooney, Daniel L.; Muldoon, Michael; Shey, Shen; Upham, Carolyn A.; Harvey, John M.; Czerwinski, Richard N.; Jordan, Michael P.; Vallières, Alexandre; Chamberland, Martin

2006-05-01

Detection performance of LWIR passive standoff chemical agent sensors is strongly influenced by various scene parameters, such as atmospheric conditions, temperature contrast, concentration-path length product (CL), agent absorption coefficient, and scene spectral variability. Although temperature contrast, CL, and agent absorption coefficient affect the detected signal in a predictable manner, fluctuations in background scene spectral radiance have less intuitive consequences. The spectral nature of the scene is not problematic in and of itself; instead it is spatial and temporal fluctuations in the scene spectral radiance that cannot be entirely corrected for with data processing. In addition, the consequence of such variability is a function of the spectral signature of the agent that is being detected and is thus different for each agent. To bracket the performance of background-limited (low sensor NEDN), passive standoff chemical sensors in the range of relevant conditions, assessment of real scene data is necessary1. Currently, such data is not widely available2. To begin to span the range of relevant scene conditions, we have acquired high fidelity scene spectral radiance measurements with a Telops FTIR imaging spectrometer 3. We have acquired data in a variety of indoor and outdoor locations at different times of day and year. Some locations include indoor office environments, airports, urban and suburban scenes, waterways, and forest. We report agent-dependent clutter measurements for three of these backgrounds.

Laser-Induced Photofragmentation Fluorescence Imaging of Alkali Compounds in Flames.

PubMed

Leffler, Tomas; Brackmann, Christian; Aldén, Marcus; Li, Zhongshan

2017-06-01

Laser-induced photofragmentation fluorescence has been investigated for the imaging of alkali compounds in premixed laminar methane-air flames. An ArF excimer laser, providing pulses of wavelength 193 nm, was used to photodissociate KCl, KOH, and NaCl molecules in the post-flame region and fluorescence from the excited atomic alkali fragment was detected. Fluorescence emission spectra showed distinct lines of the alkali atoms allowing for efficient background filtering. Temperature data from Rayleigh scattering measurements together with simulations of potassium chemistry presented in literature allowed for conclusions on the relative contributions of potassium species KOH and KCl to the detected signal. Experimental approaches for separate measurements of these components are discussed. Signal power dependence and calculated fractions of dissociated molecules indicate the saturation of the photolysis process, independent on absorption cross-section, under the experimental conditions. Quantitative KCl concentrations up to 30 parts per million (ppm) were evaluated from the fluorescence data and showed good agreement with results from ultraviolet absorption measurements. Detection limits for KCl photofragmentation fluorescence imaging of 0.5 and 1.0 ppm were determined for averaged and single-shot data, respectively. Moreover, simultaneous imaging of KCl and NaCl was demonstrated using a stereoscope with filters. The results indicate that the photofragmentation method can be employed for detailed studies of alkali chemistry in laboratory flames for validation of chemical kinetic mechanisms crucial for efficient biomass fuel utilization.

Amperometric immunosensor for α-fetoprotein antigen in human serum based on co-immobilizing dinuclear copper complex and gold nanoparticle doped chitosan film

NASA Astrophysics Data System (ADS)

Gan, Ning; Meng, Ling Hua; Wang, Feng

2009-09-01

A sensitive amperometric immunosensor for α-fetoprotein (AFP), a tumor marker for the diagnosis of hepatocellular carcinoma (HCC), was constructed, The immunosensor is prepared by co-immobilizing [Cu2(phen)2Cl2] (μ-Cl)2 (CuL), nano-Au/Chitosan(Chit) composite, horseradish peroxidase (HRP) and AFP antibody(anti-AFP) on a glassy carbon electrode (GCE). Firstly, CuL was irreversibly absorb on GCE electrode through π-π stacking interaction; then nano-Au/Chit composite was immobilized onto the electrode because of its excellent membrane-forming ability, finally HRP and anti-AFP was adsorbed onto the surface of the gold nanoparticles to construct GCE | CuL/nanoAu-chit/HRP/anti-AFP immunosensor. The preparation procedure of the electrode was characterized by electrochemical and spectroscopy method. The results showed that this immunosensor exhibited an excellent electrocatalytic response to the reduction of hydrogen peroxide (H2O2) without the aid of an electron mediator, offers a high-sensitivity (1710 nA · ng-1 · ml-1) for the detection of AFP and has good correlation for detection of AFP in the range of 0.2 to 120.0 ng/ml with a detection limit of 0.05 ng/ml. The biosensor showed high selectivity as well as good stability and reproductivity.

Remedial Investigation Report, Presidio Main Installation, Presidio of San Francisco. Volume 6: Appendices A-F

DTIC Science & Technology

1997-01-01

Version 1 .0 )9-/77 Background data analysis Az. CdB . C t_ I eF2 G S21.4 Cal-Ba Method• detection limit Mediki czi.ii- 23.6 Cl-B O.. 13.9ol DATA15 Ca...E F G H T2 4124 CoI-Cr TTL5 i.2 305 0-0 Ca=Lonomllmen97.534 Create ineprt 41.1 Cal-Cr ENTER DATA 7 J42,8251 Histogram 41.2 Wa-0 IT 42.1 Cdct Ditibto

Confocal filtering in cathodoluminescence microscopy of nanostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Narváez, Angela C., E-mail: a.c.narvaez@tudelft.nl, E-mail: j.p.hoogenboom@tudelft.nl; Weppelman, I. Gerward C.; Moerland, Robert J.

2014-06-23

Cathodoluminescence (CL) microscopy allows optical characterization of nanostructures at high spatial resolution. At the nanoscale, a main challenge of the technique is related to the background CL generated within the sample substrate. Here, we implement confocal detection of the CL signal to minimize the background contribution to the measurement. Nano-phosphors were used as point sources to evaluate the filtering capabilities of our confocal CL system, obtaining an axial intensity profile with 2.7 μm full width at half maximum for the central peak, in good correspondence with theoretical expectations. Considering the electron interaction volume, we found that the confocal filter becomes effectivemore » for electron energies above 20 keV, when using a 25 μm pinhole (0.86 Airy units). To illustrate our approach, we present confocal CL imaging of gold nanowires and triangular shaped plates deposited on an indium-tin oxide covered glass substrate, comparing the images with those obtained in standard unfiltered CL detection. The results show that confocal CL microscopy is a valuable tool for the investigation of nanostructures on highly cathodoluminescent substrates, widely used in biological and optical applications.« less

Molecular beam studies of stratospheric photochemistry

NASA Astrophysics Data System (ADS)

Moore, Teresa Anne

1998-12-01

Photochemistry of chlorine oxide containing species plays a major role in stratospheric ozone depletion. This thesis discusses two photodissociation studies of the key molecules ClONO2 and ClOOCl which were previously thought to only produce Cl-atom (ozone depleting) products at wavelengths relevant to the stratosphere. The development of a molecular beam source of ClOOCl and the photodissociation dynamics of the model system Cl2O are also discussed. In the first chapter, the photochemistry of ClONO2 is examined at 308 nm using the technique of photofragment translational spectroscopy. Two primary decomposition pathways, leading to Cl + NO3 and ClO + NO2, were observed, with a lower limit of 0.33 for the relative yield of ClO. The angular distributions for both channels were anisotropic, indicating that the dissociation occurs within a rotational period. Chapter two revisits the photodissociation dynamics of Cl2O at 248 and 308 nm, on which we had previously reported preliminary findings. At 248 nm, three distinct dissociation pathways leading to Cl + ClO products were resolved. At 308 nm, the angular distribution was slightly more isotropic that previously reported, leaving open the possibility that Cl2O excited at 308 nm lives longer than a rotational period. Chapter three describes the development and optimization of a molecular beam source of ClOOCl. We utilized pulsed laser photolysis of ClA2O to generate ClO radicals, and cooled the cell to promote three body recombination to form ClOOCl. The principal components in the beam were Cl2, Cl2O, and ClOOCl. In the fourth chapter, the photodissociation dynamics of ClOOCl are investigated at 248 and 308 nm. We observed multiple dissociation pathways which produced ClO + ClO and 2Cl + O2 products. The relative Cl:ClO product yields are 1.0:0.13 and 1.0:0.20 for ClOOCl photolysis at 248 and 308 nm, respectively. The upper limit for the relative yield of the ClO + ClO channel was 0.19 at 248 nm and 0.31 at 308 nm. These results substantially confirm the current assumption but decrease somewhat the efficiency of the ClOOCl ozone-depleting catalytic cycle. At 248 nm, ClOOCl photolysis exhibited novel dissociation dynamics which appeared to depend on the symmetry of the excited state.

Controllable preparation of copper phthalocyanine single crystal nano column and its chlorine gas sensing properties

NASA Astrophysics Data System (ADS)

Zhao, Jianhong; Qiao, Zhenfang; Zhang, Yumin; Zou, Taoyu; Yu, Leiming; Luo, Li; Wang, Xiaoyan; Yang, Yiji; Wang, Hai; Tang, Libin

2016-09-01

The unsubstituted copper phthalocyanine (CuPc) single crystal nano columns were fabricated for the first time as chlorine (Cl2) gas sensors in this paper. The nano columns of CuPc have been prepared on different substrates via template-free physical vapor deposition (PVD) approach. The growth mechanism of CuPc nano column on quartz was explored and the same condition used on other substrates including glass, sapphire (C-plane<0001>, M-plane<10 1 ¯ 0 >, R-plane<1 1 ¯ 02 >), Si and SiO2/Si came to a same conclusion, which confirmed that the aligned growth of CuPc nano column is not substrate-dependent. And then the CuPc nano column with special morphology was integrated as in-situ sensor device which exhibits high sensitivity and selectivity towards Cl2 at room temperature with a minimum detection limit as low as 0.08 ppm. The response of sensor was found to increase linearly (26 ˜659 % ) with the increase for Cl2 within concentration range (0.08 ˜4.0 ppm ) . These results clearly demonstrate the great potential of the nano column growth and device integration approach for sensor device.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Branch, Shirmir D.; Lines, Amanda M.; Lynch, John

The electrochemical and spectroelectrochemical applications of an optically transparent thin film electrode chip are investigated. The working electrode is composed of indium tin oxide (ITO); the counter and quasi-reference electrodes are composed of platinum. The stability of the platinum quasi-reference electrode is modified by coating it with a planar, solid state Ag/AgCl layer. The Ag/AgCl reference is characterized with scanning electron microscopy and energy-dispersive X-ray spectroscopy. Open circuit potential measurements indicate that the potential of the planar Ag/AgCl electrode varies a maximum of 20 mV over four days. Cyclic voltammetry measurements show that the electrode chip is comparable to amore » standard electrochemical cell. Randles-Sevcik analysis of 10 mM K3[Fe(CN)6] in 0.1 M KCl using the electrode chip shows a diffusion coefficient of 1.59 × 10-6 cm2/s, in comparison to the standard electrochemical cell value of 2.38 × 10-6 cm2/s. By using the electrode chip in an optically transparent thin layer electrode (OTTLE), the spectroelectrochemical modulation of [Ru(bpy)3]2+ florescence was demonstrated, achieving a detection limit of 36 nM.« less

Evidence for Bouncing Evolution Before Inflation After BICEP2

NASA Astrophysics Data System (ADS)

Xia, Jun-Qing; Cai, Yi-Fu; Li, Hong; Zhang, Xinmin

2014-06-01

The BICEP2 Collaboration reports a detection of primordial cosmic microwave background (CMB) B mode with a tensor-to-scalar ratio r =0.20-0.05+0.07 (68% C.L.). However, this result disagrees with the recent Planck limit r<0.11 (95% C.L.) on constraining inflation models. In this Letter we consider an inflationary cosmology with a preceding nonsingular bounce, which gives rise to observable signatures on primordial perturbations. One interesting phenomenon is that both the primordial scalar and tensor modes can have a step feature on their power spectra, which nicely cancels the tensor excess power on the CMB temperature power spectrum. By performing a global analysis, we obtain the 68% C.L. constraints on the parameters of the model from the Planck+WP and BICEP2 data together: the jump scale log10(kB/Mpc-1)=-2.4±0.2 and the spectrum amplitude ratio of bounce to inflation rB≡Pm/As=0.71±0.09. Our result reveals that the bounce inflation scenario can simultaneously explain the Planck and BICEP2 observations better than the standard cold dark matter model with a cosmological constant, and can be verified by future CMB polarization measurements.

Dark matter line emission constraints from NuSTAR observations of the bullet cluster

DOE PAGES

Riemer-Sørensen, S.; Wik, D.; Madejski, G.; ...

2015-08-27

Some dark matter candidates, e.g., sterile neutrinos, provide observable signatures in the form of mono-energetic line emission. Here, we present the first search for dark matter line emission in themore » $$3-80\\;\\mathrm{keV}$$ range in a pointed observation of the Bullet Cluster with NuSTAR. We do not detect any significant line emission and instead we derive upper limits (95% CL) on the flux, and interpret these constraints in the context of sterile neutrinos and more generic dark matter candidates. NuSTAR does not have the sensitivity to constrain the recently claimed line detection at $$3.5\\;\\mathrm{keV}$$, but improves on the constraints for energies of $$10-25\\;\\mathrm{keV}$$.« less

Comparison of the Microbicidal activity of monochloramine and iodine.

PubMed

Arnitz, R; Nagl, M; Gottardi, W

2015-12-01

Recently, we showed that monochloramine (NH2 Cl) has a significantly stronger bactericidal and fungicidal activity than chloramine T despite its lower oxidizing power. This phenomenon was explained by increased penetration because of the higher lipophilicity and smaller bulk of NH2 Cl. As iodine (I2 ) has an even fivefold higher bulk than NH2 Cl, a comparison of both compounds regarding their microbicidal activity became the aim of this study. Aqueous solutions of I2 at a concentration of 10·7 μmol l(-1) killed 10(6) colony forming units per millilitre (CFU ml(-1) ) of Escherichia coli, Staphylococcus aureus or Pseudomonas aeruginosa to the detection limit of 10(2) CFU ml(-1) within 1 min at 20°C and pH 7·1, while a concentration of 36-355 μmol l(-1) of NH2 Cl was needed to achieve the same effect. Aspergillus fumigatus was inactivated within 5 min by 36 μmol l(-1) I2 and by 355 μmol l(-1) NH2 Cl, Candida albicans within 1 min by 10·7 μmol l(-1) I2 and by 355 μmol l(-1) NH2 Cl. The lipophilicity of I2 , determined with the octanol/water method, was three powers of 10 higher than that of NH2 Cl. The at least 10-fold stronger microbicidal activity of iodine suggests that the hindrance of penetration of the bulky molecule is outweighed by enhanced lipophilicity. The microbicidal activity of active halogen compounds increases not only with their reactivity, but also with higher lipophilicity and lower bulk, as shown recently. In this study, iodine showed a higher microbicidal activity than monochloramine and a 1000-fold higher lipophilicity. Therefore, the lipophilicity of a disinfectant may be more important than the bulk for bactericidal activity. These facts should be considered upon the design of new antiseptics and their clinical application. © 2015 The Society for Applied Microbiology.

Early Detection of Salt Stress Damage by Biophotons in Red Bean Seedling

NASA Astrophysics Data System (ADS)

Ohya, Tomoyuki; Kurashige, Hideaki; Okabe, Hirotaka; Kai, Shoichi

2000-06-01

The optical detection of the stress damage to plants by NaCl solutions was attempted during germination of a seed and growth of a root. We compared the photon intensity of red beans before and after NaCl treatment and found that the photon intensity after NaCl treatment decreased as the NaCl concentration increased. For the saturated NaCl concentration (4.5 M), however, the observed photon intensity drastically increased, and the simultaneous destruction of cell membranes was observed. The intensity of biophoton emission from red beans showed characteristic change with salt concentrations. When the salt stress was applied to the red beans at an early growth stage, their root elongations were suppressed and photon intensity from the root decreased. This was not the case for the root at the late stage. This shows that biophoton intensity due to salt stress depends on not only NaCl concentration but also the growth stage of the plant. We may conclude that the extent of damage to roots by salt stress can be evaluated from biophoton response.

Lithium fluxes indicate presence of Na-Cl cotransport (NCC) in human lens epithelial cells.

PubMed

Lauf, Peter K; Chimote, Ameet A; Adragna, Norma C

2008-01-01

During regulatory volume decrease (RVD) of human lens epithelial cells (hLECs) by clotrimazole (CTZ)-sensitive K fluxes, Na-K-2Cl cotransport (NKCC) remains active and K-Cl cotransport (KCC) inactive. To determine whether such an abnormal behavior was caused by RVD-induced cell shrinkage, NKCC was measured in the presence of either CTZ or in high K media to prevent RVD. NKCC transports RbCl + NaCl, and LiCl + KCl; thus ouabain-insensitive, bumetanide-sensitive (BS) or Cl-dependent (ClD) Rb and Li fluxes were determined in hyposmotic high NaCl media with CTZ, or in high KCl media alone, or with sulfamate (Sf) or nitrate as Cl replacement at varying Rb, Li or Cl mol fractions (MF). Unexpectedly, NKCC was inhibited by 80% with CTZ (IC(50) = 31 microM). In isosmotic (300 mOsM) K, Li influx was approximately 1/3 of Rb influx in Na, 50% lower in Sf, and bumetanide-insensitive (BI). In hypotonic (200 mOsM) K, only the ClD but not BS Li fluxes were detected. At Li MFs from 0.1-1, Li fluxes fitted a bell-shaped curve maxing at approximately 0.6 Li MF, with the BS fluxes equaling approximately 1/4 of the ClD-Li influx. The difference, i.e. the BI/ClD Li influx, saturated with increasing Li and Cl MFs, with K(ms) for Li of 11 with, and 7 mM without K, and of approximately 46 mM for Cl. Inhibition of this K-independent Li influx by thiazides was weak whilst furosemide (<100 microM) was ineffective. Reverse transcription polymerase chain reaction and Western blots verified presence of both NKCC1 and Na-Cl cotransport (NCC). In conclusion, in hyposmotic high K media, which prevents CTZ-sensitive K flux-mediated RVD in hLECs, NKCC1, though molecularly expressed, was functionally silent. However, a K-independent and moderately thiazide-sensitive ClD-Li flux, i.e. LiCC, likely occurring through NCC was detected operationally and molecularly. (c) 2008 S. Karger AG, Basel.

Computational and experimental study of the interactions between ionic liquids and volatile organic compounds.

PubMed

Gao, Tingting; Andino, Jean M; Alvarez-Idaboy, J Raul

2010-09-07

Computational chemistry calculations were performed to investigate the interactions of ionic liquids with different classes of volatile organic compounds (VOCs), including alcohols, aldehydes, ketones, alkanes, alkenes, alkynes and aromatic compounds. At least one VOC was studied to represent each class. Initially, 1-butyl-3-methylimindazolium chloride (abbreviated as C(4)mimCl) was used as the test ionic liquid compound. Calculated interaction lengths between atoms in the ionic liquid and the VOC tested as well as thermodynamic data suggest that C(4)mimCl preferentially interacts with alcohols as compared to other classes of volatile organic compounds. The interactions of methanol with different kinds of ionic liquids, specifically 1-butyl-3-methylimidazolium bromine (C(4)mimBr) and 1-butyl-3-methylimidazolium tetrafluoroborate (C(4)mimBF(4)) were also studied. In comparing C(4)mimCl, C(4)mimBr, and C(4)mimBF(4), the computational results suggest that C(4)mimCl is more likely to interact with methanol. Laboratory experiments were performed to provide further evidence for the interaction between C(4)mimCl and different classes of VOCs. Fourier transform infrared spectroscopy was used to probe the ionic liquid surface before and after exposure to the VOCs that were tested. New spectral features were detected after exposure of C(4)mimCl to various alcohols. The new features are characteristic of the alcohols tested. No new IR features were detected after exposure of the C(4)mimCl to the aldehyde, ketone, alkane, alkene, alkyne or aromatic compounds studied. In addition, after exposing the C(4)mimCl to a multi-component mixture of various classes of compounds (including an alcohol), the only new peaks that were detected were characteristic of the alcohol that was tested. These experimental results demonstrated that C(4)mimCl is selective to alcohols, even in complex mixtures. The findings in this work provide information for future gas-phase alcohol sensor design.

Search for the permanent electric dipole moment of 129Xe

NASA Astrophysics Data System (ADS)

Sachdeva, Natasha; Chupp, Timothy; Gong, Fei; Babcock, Earl; Salhi, Zahir; Burghoff, Martin; Fan, Isaac; Killian, Wolfgang; Knappe-Grüneberg, Silvia; Schabel, Allard; Seifert, Frank; Trahms, Lutz; Voigt, Jens; Degenkolb, Skyler; Fierlinger, Peter; Krägeloh, Eva; Lins, Tobias; Marino, Michael; Meinel, Jonas; Niessen, Benjamin; Stuiber, Stefan; Terrano, William; Kuchler, Florian; Singh, Jaideep

2017-09-01

CP-violation in Beyond-the-Standard-Model physics, necessary to explain the baryon asymmetry, gives rise to permanent electric dipole moments (EDMs). EDM measurements of the neutron, electron, paramagnetic and diamagnetic atoms constrain CP-violating parameters. The current limit for the 129Xe EDM is 6 ×10-27 e . cm (95 % CL). The HeXeEDM experiment at FRM-II (Munich Research Reactor) and BMSR-2 (Berlin Magnetically Shielded Room) uses a stable magnetic field in a magnetically shielded room and 3He comagnetometer with potential to improve the limit by two orders of magnitude. Polarized 3He and 129Xe free precession is detected with SQUID magnetometers in the presence of applied electric and magnetic fields. Conclusions from recent measurements will be presented.

Search for Dinucleon Decay into Kaons in Super-Kamiokande

NASA Astrophysics Data System (ADS)

Litos, M.; Abe, K.; Hayato, Y.; Iida, T.; Ikeda, M.; Iyogi, K.; Kameda, J.; Kobayashi, K.; Koshio, Y.; Kozuma, Y.; Miura, M.; Moriyama, S.; Nakahata, M.; Nakayama, S.; Obayashi, Y.; Ogawa, H.; Sekiya, H.; Shiozawa, M.; Suzuki, Y.; Takeda, A.; Takenaga, Y.; Takeuchi, Y.; Ueno, K.; Ueshima, K.; Watanabe, H.; Yamada, S.; Yokozawa, T.; Hazama, S.; Ishihara, C.; Kaji, H.; Kajita, T.; Kaneyuki, K.; McLachlan, T.; Okumura, K.; Shimizu, Y.; Tanimoto, N.; Vagins, M. R.; Kearns, E.; Stone, J. L.; Sulak, L. R.; Dufour, F.; Raaf, J. L.; Henning, B.; Goldhaber, M.; Bays, K.; Casper, D.; Cravens, J. P.; Kropp, W. R.; Mine, S.; Regis, C.; Smy, M. B.; Sobel, H. W.; Ganezer, K. S.; Hill, J.; Keig, W. E.; Jang, J. S.; Kim, J. Y.; Lim, I. T.; Albert, J. B.; Wongjirad, T.; Wendell, R.; Scholberg, K.; Walter, C. W.; Tasaka, S.; Learned, J. G.; Matsuno, S.; Watanabe, Y.; Hasegawa, T.; Ishida, T.; Ishii, T.; Kobayashi, T.; Nakadaira, T.; Nakamura, K.; Nishikawa, K.; Nishino, H.; Oyama, Y.; Sakashita, K.; Sekiguchi, T.; Tsukamoto, T.; Suzuki, A. T.; Minamino, A.; Nakaya, T.; Fukuda, Y.; Itow, Y.; Mitsuka, G.; Tanaka, T.; Jung, C. K.; Lopez, G.; McGrew, C.; Terri, R.; Yanagisawa, C.; Tamura, N.; Ishino, H.; Kibayashi, A.; Mino, S.; Mori, T.; Sakuda, M.; Toyota, H.; Kuno, Y.; Yoshida, M.; Kim, S. B.; Yang, B. S.; Ishizuka, T.; Okazawa, H.; Choi, Y.; Nishijima, K.; Yokosawa, Y.; Koshiba, M.; Yokoyama, M.; Totsuka, Y.; Chen, S.; Heng, Y.; Yang, Z.; Zhang, H.; Kielczewska, D.; Mijakowski, P.; Connolly, K.; Dziomba, M.; Thrane, E.; Wilkes, R. J.; Super-Kamiokande Collaboration

2014-04-01

A search for the dinucleon decay pp→K+K+ has been performed using 91.6 kton .yr data from Super-Kamiokande-I. This decay provides a sensitive probe of the R-parity-violating parameter λ112''. A boosted decision tree analysis found no signal candidates in the data. The expected background was 0.28±0.19 atmospheric neutrino induced events and the estimated signal detection efficiency was 12.6%±3.2%. A lower limit of 1.7×1032 years has been placed on the partial lifetime of the decay O16→C14K+K+ at 90% C.L. A corresponding upper limit of 7.8×10-9 has been placed on the parameter λ112''.

Ultrasound Current Source Density Imaging in live rabbit hearts using clinical intracardiac catheter

NASA Astrophysics Data System (ADS)

Li, Qian

Ultrasound Current Source Density Imaging (UCSDI) is a noninvasive modality for mapping electrical activities in the body (brain and heart) in 4-dimensions (space + time). Conventional cardiac mapping technologies for guiding the radiofrequency ablation procedure for treatment of cardiac arrhythmias have certain limitations. UCSDI can potentially overcome these limitations and enhance the electrophysiology mapping of the heart. UCSDI exploits the acoustoelectric (AE) effect, an interaction between ultrasound pressure and electrical resistivity. When an ultrasound beam intersects a current path in a material, the local resistivity of the material is modulated by the ultrasonic pressure, and a change in voltage signal can be detected based on Ohm's Law. The degree of modulation is determined by the AE interaction constant K. K is a fundamental property of any type of material, and directly affects the amplitude of the AE signal detected in UCSDI. UCSDI requires detecting a small AE signal associated with electrocardiogram. So sensitivity becomes a major challenge for transferring UCSDI to the clinic. This dissertation will determine the limits of sensitivity and resolution for UCSDI, balancing the tradeoff between them by finding the optimal parameters for electrical cardiac mapping, and finally test the optimized system in a realistic setting. This work begins by describing a technique for measuring K, the AE interaction constant, in ionic solution and biological tissue, and reporting the value of K in excised rabbit cardiac tissue for the first time. K was found to be strongly dependent on concentration for the divalent salt CuSO4, but not for the monovalent salt NaCl, consistent with their different chemical properties. In the rabbit heart tissue, K was determined to be 0.041 +/- 0.012 %/MPa, similar to the measurement of K in physiologic saline: 0.034 +/- 0.003 %/MPa. Next, this dissertation investigates the sensitivity limit of UCSDI by quantifying the relation between the recording electrode distance and the measured AE signal amplitude in gel phantoms and excised porcine heart tissue using a clinical intracardiac catheter. Sensitivity of UCSDI with catheter was 4.7 microV/mA (R2 = 0.999) in cylindrical gel (0.9% NaCl), and 3.2 microV/mA (R2 = 0.92) in porcine heart tissue. The AE signal was detectable more than 25 mm away from the source in cylindrical gel (0.9% NaCl). Effect of transducer properties on UCSDI sensitivity is also investigated using simulation. The optimal ultrasound transducer parameters chosen for cardiac imaging are center frequency = 0.5 MHz and f/number = 1.4. Last but not least, this dissertation shows the result of implementing the optimized ultrasound parameters in live rabbit heart preparation, the comparison of different recording electrode configuration and multichannel UCSDI recording and reconstruction. The AE signal detected using the 0.5 MHz transducer was much stronger (2.99 microV/MPa) than the 1.0 MHz transducer (0.42 microV/MPa). The clinical lasso catheter placed on the epicardium exhibited excellent sensitivity without being too invasive. 3-dimensional cardiac activation maps of the live rabbit heart using only one pair of recording electrodes were also demonstrated for the first time. Cardiac conduction velocity for atrial (1.31 m/s) and apical (0.67 m/s) pacing were calculated based on the activation maps. The future outlook of this dissertation includes integrating UCSDI with 2-dimensional ultrasound transducer array for fast imaging, and developing a multi-modality catheter with 4-dimensional UCSDI, multi-electrode recording and echocardiography capacity.

Advances in Constraining Solubilities of H-O-C-S-Cl-bearing Fluids in Silicate Melts

NASA Astrophysics Data System (ADS)

Webster, J. D.

2009-12-01

Magmatic-hydrothermal fluids that are variably enriched in the volatile components H2O, CO2/CH4, H2S/SO2, Cl, F, ± B alter rock; dissolve, transport, and deposit ore metals, and drive volcanism. The efficacy of these processes varies directly with the compositions and quantities, and in particular, with the molar volumes of the fluids involved. Although natural hydrothermal fluids are geochemically diverse, experimental constraints on volatile solubilities in silicate melts are largely limited to two volatiles. Recent experimental research, however, has begun to address mutual solubility relationships of three and four volatiles in felsic to intermediate aluminosilicate melts at shallow crustal pressures. Following well-established correlations demonstrating that as little as a few hundred to thousand ppm CO2 or Cl reduce H2O solubility in melts, and hence enhance the tendency for magma to exsolve one or two fluid phases, recent work shows fundamentally important solubility relationships involving H2O, S, and Cl. Research on rhyodacitic (Botcharnikov et al., 2004) and phonolitic melts at 200 MPa reveals that hundreds to thousands of ppm S will reduce Cl solubility in these melts. Thus, S reduces Cl solubility, which in turn reduces H2O solubility in melts. Other investigations have determined that CaSO4 solubility in oxidizing hydrothermal fluids varies directly with the concentrations of NaCl ± KCl in these fluids (Newton and Manning, 2005; Webster et al., 2009). The CaSO4 contents in the most alkali chloride-enriched fluids exceed 60 wt.%. It follows that some mineralizing saline magmatic fluids are strongly enriched in Ca, Na, K, Cl, SO4, and reduced S species. Research on H2O-, CO2-, and Cl-bearing melts at 200 MPa also highlights critical reciprocal volatile solubility behavior. Work at 1200°C on andesitic melts saturated in two fluids determines that the presence of CO2 enlarges the immiscibility gap for vapor plus brine and increases the activities of H2O and Cl (Botcharnikov et al. 2007). Conversely, other work involving Cl-enriched phonolitic melts plus two fluids at 900°C observes that the presence of Cl strongly reduces CO2 solubility in the melt. In fact, for runs containing as much as 80 mole percent CO2 in the fluid, the CO2/CO3 contents of the melts were reduced to values below the limit of detection for FTIR (< ca. 30-40 ppm). Thus, Cl works to reduce CO2 solubility, which in turn reduces H2O solubility in phonolitic melts. Current work on the solubility of H-O-C-S in haplogranitic melts at 200 MPa demonstrates that the addition of C reduces the (fluid/melt) partition coefficient for S. In addition, these experimentally determined partition coefficients decrease in the order CO2 > S > H2O, and their ranges are virtually identical to and thus confirm modeled values computed (Scaillet and Pichavant, 2003) for pre-eruptive magmatic fluids based on volatile fugacities of volcanic gases of arc-related magmas. Botcharnikov R et al (2004) Chem. Geol. 213, 207-225. Botcharnikov R, Holtz F, Behrens H (2007) Eur. J. Mineral. 19, 671-680. Newton R, Manning C (2005) J. Petrol. 46, 701-716. Scaillet B, Pichavant M (2003) Volcanic Degassing, Geol. Soc. Spec. Pub. 213, 23-52. Webster J, Sintoni M, De Vivo B (2009) Chem. Geol. 263, 19-36.

Augury of darkness: the low-mass dark Z' portal

DOE PAGES

Alves, Alexandre; Arcadi, Giorgio; Mambrini, Yann; ...

2017-04-28

Dirac fermion dark matter models with heavy Z' mediators are subject to stringent constraints from spin-independent direct searches and from LHC bounds, cornering them to live near the Z' resonance. Such constraints can be relaxed, however, by turning off the vector coupling to Standard Model fermions, thus weakening direct detection bounds, or by resorting to light Z' masses, below the Z pole, to escape heavy resonance searches at the LHC. In this work we investigate both cases, as well as the applicability of our findings to Majorana dark matter. We derive collider bounds for light Z' gauge bosons using themore » CL S method, spin-dependent scattering limits, as well as the spin-independent scattering rate arising from the evolution of couplings between the energy scale of the mediator mass and the nuclear energy scale, and indirect detection limits. In conclusion, we show that such scenarios are still rather constrained by data, and that near resonance they could accommodate the gamma-ray GeV excess in the Galactic center.« less

Impact of Contact Lens Material, Design, and Fitting on Discomfort.

PubMed

Stapleton, Fiona; Tan, Jacqueline

2017-01-01

To review the effect of contact lens (CL) material, design, and fitting characteristics on CL discomfort. A PubMed search identified publications describing subjective comfort and CL material, fitting, and design parameters. The review included clinical signs associated with discomfort that may be a consequence of these parameters. Reduced lens movement or more CL tightness were associated with improved comfort. Increased lens-induced paralimbal conjunctival staining and indentation, considered as quasi-indicators of CL fitting or edge design, were also associated with better comfort. No recent studies have evaluated varying CL design parameters and subjective comfort. Silicone hydrogel CLs are no different in comfort compared with hydrogel CLs. Lower equilibrium water content is associated with improved comfort in hydrogel CL wear. Coefficient of friction shows promise as a material factor potentially associated with comfort. Lid wiper epitheliopathy and lid-parallel conjunctival folds have been linked with comfort in established wearers. Recent studies have confirmed the association between more mobile CLs and more discomfort, whereas closer conformity of the CL to the bulbar conjunctiva improved subjective comfort. There is no evidence to support the perceived comfort difference between silicone hydrogel and hydrogel CL. There has been limited progress in understanding the impact of varying specific CL design parameters. Although specific clinical signs may be predictive of discomfort, their role in the natural history of discomfort remains unclear. A better understanding of the relationship between coefficient of friction and comfort and strategies to improve lubricity may hold promise for limiting CL discomfort.

Ammonium chloride salting out extraction/cleanup for trace-level quantitative analysis in food and biological matrices by flow injection tandem mass spectrometry.

PubMed

Nanita, Sergio C; Padivitage, Nilusha L T

2013-03-20

A sample extraction and purification procedure that uses ammonium-salt-induced acetonitrile/water phase separation was developed and demonstrated to be compatible with the recently reported method for pesticide residue analysis based on fast extraction and dilution flow injection mass spectrometry (FED-FI-MS). The ammonium salts evaluated were chloride, acetate, formate, carbonate, and sulfate. A mixture of NaCl and MgSO4, salts used in the well-known QuEChERS method, was also tested for comparison. With thermal decomposition/evaporation temperature of <350°C, ammonium salts resulted in negligible ion source residual under typical electrospray conditions, leading to consistent method performance and less instrument cleaning. Although all ammonium salts tested induced acetonitrile/water phase separation, NH4Cl yielded the best performance, thus it was the preferred salting out agent. The NH4Cl salting out method was successfully coupled with FI/MS/MS and tested for fourteen pesticide active ingredients: chlorantraniliprole, cyantraniliprole, chlorimuron ethyl, oxamyl, methomyl, sulfometuron methyl, chlorsulfuron, triflusulfuron methyl, azimsulfuron, flupyrsulfuron methyl, aminocyclopyrachlor, aminocyclopyrachlor methyl, diuron and hexazinone. A validation study was conducted with nine complex matrices: sorghum, rice, grapefruit, canola, milk, eggs, beef, urine and blood plasma. The method is applicable to all analytes, except aminocyclopyrachlor. The method was deemed appropriate for quantitative analysis in 114 out of 126 analyte/matrix cases tested (applicability rate=0.90). The NH4Cl salting out extraction/cleanup allowed expansion of FI/MS/MS for analysis in food of plant and animal origin, and body fluids with increased ruggedness and sensitivity, while maintaining high-throughput (run time=30s/sample). Limits of quantitation (LOQs) of 0.01mgkg(-1) (ppm), the 'well-accepted standard' in pesticide residue analysis, were achieved in >80% of cases tested; while limits of detection (LODs) were typically in the range of 0.001-0.01mgkg(-1) (ppm). A comparison to a well-established HPLC/MS/MS method was also conducted, yielding comparable results, thus confirming the suitability of NH4Cl salting out FI/MS/MS for pesticide residue analysis. Copyright © 2013 Elsevier B.V. All rights reserved.

In vitro degradation of hexanitrohexaazaisowurtzitane (CL-20) by cytosolic enzymes of Japanese quail and the rabbit.

PubMed

Bardai, Ghalib K; Halasz, Annamaria; Sunahara, Geoffrey I; Dodard, Sabine; Spear, Philip A; Grosse, Stephan; Hoang, Johnston; Hawari, Jalal

2006-12-01

Hexanitrohexaazaisowurtzitane (CL-20) is a polycyclic nitramine explosive and propellant, currently being considered as a potential replacement for existing cyclic nitramine explosives. Earlier studies have provided evidence suggestive of adverse liver effects in adult Coturnix spp. exposed to CL-20, yet analysis of tissue samples (plasma, liver, brain, heart, or spleen) indicated that CL-20 was not detectable in these treated animals. The present study was conducted to identify and purify the enzymes capable of CL-20 biotransformation. Results indicate that the hepatic biotransformation of CL-20 in vitro was inhibited by ethacrynic acid (93%) and by the glutathione (GSH) analogue S-octylglutathione (80%), suggesting the involvement of glutathione-S-transferase (GST). Partially purified cytosolic alpha- and mu-type GST (requiring presence of GSH as a cofactor) from quail and rabbit liver was capable of CL-20 biotransformation. The degradation of CL-20 (0.30 +/- 0.05 and 0.40 +/- 0.02 nmol/min/mg protein for quail and rabbit, respectively) was accompanied with the formation of nitrite and consumption of GSH. Using liquid chromatography/mass spectrometry, we detected two intermediates, that is, open-ring, monodenitrated GSH-conjugated CL-20 biotransformation product with the same deprotonated molecular mass ion at 699 Da, suggesting isomeric forms of the intermediate metabolites. Identity of the conjugated metabolites was confirmed by using ring-labeled [15N]CL-20 and the nitro group-labeled [15NO2]CL-20. These data suggest that the in vitro biotransformation of CL-20 by GST under the conditions tested may be a key initial step in the in vivo degradation of CL-20 in the quail and resulted in the formation of more biologically reactive intermediates than the parent compound. These data will aid in our understanding of the biotransformation processes of CL-20 in vivo.

Phenolic Compounds and Expression of 4CL Genes in Silver Birch Clones and Pt4CL1a Lines

PubMed Central

Sutela, Suvi; Hahl, Terhi; Tiimonen, Heidi; Aronen, Tuija; Ylioja, Tiina; Laakso, Tapio; Saranpää, Pekka; Chiang, Vincent; Julkunen-Tiitto, Riitta; Häggman, Hely

2014-01-01

A small multigene family encodes 4-coumarate:CoA ligases (4CLs) catalyzing the CoA ligation of hydroxycinnamic acids, a branch point step directing metabolites to a flavonoid or monolignol pathway. In the present study, we examined the effect of antisense Populus tremuloides 4CL (Pt4CL1) to the lignin and soluble phenolic compound composition of silver birch (Betula pendula) Pt4CL1a lines in comparison with non-transgenic silver birch clones. The endogenous expression of silver birch 4CL genes was recorded in the stems and leaves and also in leaves that were mechanically injured. In one of the transgenic Pt4CL1a lines, the ratio of syringyl (S) and guaiacyl (G) lignin units was increased. Moreover, the transcript levels of putative silver birch 4CL gene (Bp4CL1) were reduced and contents of cinnamic acid derivatives altered. In the other two Pt4CL1a lines changes were detected in the level of individual phenolic compounds. However, considerable variation was found in the transcript levels of silver birch 4CLs as well as in the concentration of phenolic compounds among the transgenic lines and non-transgenic clones. Wounding induced the expression of Bp4CL1 and Bp4CL2 in leaves in all clones and transgenic lines, whereas the transcript levels of Bp4CL3 and Bp4CL4 remained unchanged. Moreover, minor changes were detected in the concentrations of phenolic compounds caused by wounding. As an overall trend the wounding decreased the flavonoid content in silver birches and increased the content of soluble condensed tannins. The results indicate that by reducing the Bp4CL1 transcript levels lignin composition could be modified. However, the alterations found among the Pt4CL1a lines and the non-transgenic clones were within the natural variation of silver birches, as shown in the present study by the clonal differences in the transcripts levels of 4CL genes, soluble phenolic compounds and condensed tannins. PMID:25502441

Field data analysis of active chlorine-containing stormwater samples.

PubMed

Zhang, Qianyi; Gaafar, Mohamed; Yang, Rong-Cai; Ding, Chen; Davies, Evan G R; Bolton, James R; Liu, Yang

2018-01-15

Many municipalities in Canada and all over the world use chloramination for drinking water secondary disinfection to avoid DBPs formation from conventional chlorination. However, the long-lasting monochloramine (NH 2 Cl) disinfectant can pose a significant risk to aquatic life through its introduction into municipal storm sewer systems and thus fresh water sources by residential, commercial, and industrial water uses. To establish general total active chlorine (TAC) concentrations in discharges from storm sewers, the TAC concentration was measured in stormwater samples in Edmonton, Alberta, Canada, during the summers of 2015 and 2016 under both dry and wet weather conditions. The field-sampling results showed TAC concentration variations from 0.02 to 0.77 mg/L in summer 2015, which exceeds the discharge effluent limit of 0.02 mg/L. As compared to 2015, the TAC concentrations were significantly lower during the summer 2016 (0-0.24 mg/L), for which it is believed that the higher precipitation during summer 2016 reduced outdoor tap water uses. Since many other cities also use chloramines as disinfectants for drinking water disinfection, the TAC analysis from Edmonton may prove useful for other regions as well. Other physicochemical and biological characteristics of stormwater and storm sewer biofilm samples were also analyzed, and no significant difference was found during these two years. Higher density of AOB and NOB detected in the storm sewer biofilm of residential areas - as compared with other areas - generally correlated to high concentrations of ammonium and nitrite in this region in both of the two years, and they may have contributed to the TAC decay in the storm sewers. The NH 2 Cl decay laboratory experiments illustrate that dissolved organic carbon (DOC) concentration is the dominant factor in determining the NH 2 Cl decay rate in stormwater samples. The high DOC concentrations detected from a downstream industrial sampling location may contribute to a high stormwater NH 2 Cl decay rate in this area. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effects of the background electrolyte on Th(IV) sorption to muscovite mica

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schmidt, Moritz; Hellebrandt, Stefan; Knope, Karah E.

2015-09-01

The adsorption of tetravalent thorium on the muscovite mica (001) basal plane was studied by X-ray crystal truncation rod (CTR), and resonant anomalous X-ray reflectivity (RAXR) measurements and alpha spectrometry in the presence of perchlorate background electrolytes LiClO 4, NaClO 4, and KClO 4 ([Th(IV)] = 0.1 mM, I = 0.1 M or 0.01 M, pH = 3.3 ± 0.3). RAXR data directly reveal a strong influence of the background electrolyte on the actinide sorption. No significant Th adsorption was observed in 0.1 M NaClO 4, i.e., the Th coverage θ(Th), the number of Th per unit cell area ofmore » the muscovite surface (A UC = 46.72 Å 2), was ≤ 0.01 Th/A UC, whereas limited uptake (θ(Th) ~ 0.04 Th/A UC) was detected at a lower ionic strength (I = 0.01 M). These results are in stark contrast to the behavior of Th in 0.1 M NaCl which showed a coverage of 0.4 Th/A UC (Schmidt et al., 2012a). Th uptake was also influenced by the electrolyte cation. Weak adsorption was observed in 0.1M KClO 4 (θ(Th) ~ 0.07 Th/AUC) similar to the results in NaClO 4 at lower ionic strength. In contrast, strong adsorption was found in 0.1 M LiClO 4, with θ(Th) = 4.9 Th/A UC, a ~10-fold increase compared with that previously reported in NaCl. These differences are confirmed independently by ex situ alpha spectrometry, which shows no measurable Th coverage in 0.1 M NaClO 4 background in contrast to a large coverage of 1.6 Th/A UC in 0.1 M LiClO 4. The CTR/RAXR analyses of Th-LiClO 4 show the sorption structure consisting of Th species that are broadly distributed, centered at heights of 4.1 Å and 29 Å distance from the interface. Neither the very large distribution height of the second species nor the high coverage can be explained with (hydrated) ionic adsorption, suggesting that the enhanced uptake is presumably due to the formation and sorption of Th nanoparticles.« less

Decomposition of the polycyclic nitramine explosive, CL-20, by Fe(0).

PubMed

Balakrishnan, Vimal K; Monteil-Rivera, Fanny; Halasz, Annamaria; Corbeanu, Aurelian; Hawari, Jalal

2004-12-15

CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane), C6H6N12O12, is an emerging energetic chemical that may replace RDX, but its degradation pathways are not well-known. In the present study, zerovalent iron was used to degrade CL-20 with the aim of determining its products and degradation pathways. In the absence of O2, CL-20 underwent a rapid decomposition with the concurrent formation of nitrite to ultimately produce nitrous oxide, ammonium, formate, glyoxal, and glycolate. LC/MS (ES-) showed the presence of several key products carrying important information on the initial reactions involved in the degradation of CL-20. For instance, a doubly denitrated intermediate of CL-20 was detected together with the mono- and dinitroso derivatives of the energetic chemical. Two other intermediates with [M-H]- at 392 and 376 Da, matching empirical formulas of C6H7N11O10 and C6H7N11O9, respectively, were detected. Using 15N-labeled CL-20, the two intermediates were tentatively identified as the denitrohydrogenated products of CL-20 and its mononitroso derivative, respectively. The present experimental findings suggest that CL-20 degraded via at least two initial routes: one involving denitration and the second involving sequential reduction of the N-NO2 to the corresponding nitroso (N-NO) derivatives prior to denitration and ring cleavage.

Reactivity of OH radicals with chlorobenzoic acids—A pulse radiolysis and steady-state radiolysis study

NASA Astrophysics Data System (ADS)

Zona, Robert; Solar, Sonja; Getoff, Nikola; Sehested, Knud; Holcman, Jerzy

2010-05-01

The reactions of OH radicals with 2-, 3-, 4-chlorobenzoic acids (ClBzA) and chlorobenzene (ClBz), k( rad OH+substrates)=(4.5-6.2)×10 9 dm 3 mol -1 s -1, have been studied by pulse radiolysis in N 2O saturated solutions. The absorption maxima of the OH-adducts were in the range of 320-340 nm. Their decay was according to a second-order reaction, 2 k=(1-9)×10 8 dm 3 mol -1 s -1. In the presence of N 2O/O 2 the formation of peroxyl radicals was detectable for 2-, 4-ClBzA and ClBz, k(OH-adduct+O 2)=(2-4)×10 7 dm 3 mol -1 s -1, while this reaction for 3-ClBzA was too slow to be registered. In the presence of N 2O the degradation rates induced by gamma radiation were very similar for all chlorobenzoic acids, yet the chloride formation was distinctly higher for 3-ClBzA. In the presence of oxygen the initial degradation of 2-and 4-ClBzA equaled the OH-radical concentration, whereas in case of 3-ClBzA only ˜60% of rad OH led to degradation. The order for the efficiency of dehalogenation was 4->2->3-ClBzA. Several primary radiolytic products could be detected by HPLC. To evaluate the toxicity of final products a bacterial bioluminescence test was carried out.

Measuring The cmb Polarization At 94 GHz With The QUIET Pseudo-cL Pipeline

NASA Astrophysics Data System (ADS)

Buder, Immanuel; QUIET Collaboration

2012-01-01

The Q/U Imaging ExperimenT (QUIET) aims to limit or detect cosmic microwave background (CMB) B-mode polarization from inflation. This talk is part of a 3-talk series on QUIET. The previous talk describes the QUIET science and instrument. QUIET has two parallel analysis pipelines which are part of an effort to validate the analysis and confirm the result. In this talk, I will describe the analysis methods of one of these: the pseudo-Cl pipeline. Calibration, noise modeling, filtering, and data-selection choices are made following a blind-analysis strategy. Central to this strategy is a suite of 30 null tests, each motivated by a possible instrumental problem or systematic effect. The systematic errors are also evaluated through full-season simulations in the blind stage of the analysis before the result is known. The CMB power spectra are calculated using a pseudo-Cl cross-correlation technique which suppresses contamination and makes the result insensitive to noise bias. QUIET will detect the first three peaks of the even-parity (E-mode) spectrum at high significance. I will show forecasts of the systematic errors for these results and for the upper limit on B-mode polarization. The very low systematic errors in these forecasts show that the technology is ready to be applied in a more sensitive next-generation experiment. The next and final talk in this series covers the other parallel analysis pipeline, based on maximum likelihood methods. This work was supported by NSF and the Department of Education.

The single evolutionary origin of chlorinated auxin provides a phylogenetically informative trait in the Fabaceae.

PubMed

Lam, Hong Kiat; Ross, John J; McAdam, Erin L; McAdam, Scott A M

2016-07-02

Chlorinated auxin (4-chloroindole-3-acetic acid, 4-Cl-IAA), a highly potent plant hormone, was once thought to be restricted to species of the tribe Fabeae within the Fabaceae, until we recently detected this hormone in the seeds of Medicago, Melilotus and Trifolium species. The absence of 4-Cl-IAA in the seeds of the cultivated species Cicer aeritinum from the Cicerae tribe, immediately basal to the Fabeae and Trifolieae tribes, suggested a single evolutionary origin of 4-Cl-IAA. Here, we provide a more robust phylogenetic placement of the ability to produce chlorinated auxin by screening key species spanning this evolutionary transition. We report no detectable level of 4-Cl-IAA in Cicer echinospermum (a wild relative of C. aeritinum) and 4 species (Galega officinalis, Parochetus communis, Astragalus propinquus and A. sinicus) from tribes or clades more basal or sister to the Cicerae tribe. We did detect 4-Cl-IAA in the dry seeds of 4 species from the genus Ononis that are either basal to the genera Medicago, Melilotus and Trigonella or basal to, but still within, the Fabeae and Trifolieae (ex. Parochetus) clades. We conclude that the single evolutionary origin of this hormone in seeds can be used as a phylogenetically informative trait within the Fabaceae.

The single evolutionary origin of chlorinated auxin provides a phylogenetically informative trait in the Fabaceae

PubMed Central

Lam, Hong Kiat; Ross, John J.; McAdam, Erin L.; McAdam, Scott A. M.

2016-01-01

ABSTRACT Chlorinated auxin (4-chloroindole-3-acetic acid, 4-Cl-IAA), a highly potent plant hormone, was once thought to be restricted to species of the tribe Fabeae within the Fabaceae, until we recently detected this hormone in the seeds of Medicago, Melilotus and Trifolium species. The absence of 4-Cl-IAA in the seeds of the cultivated species Cicer aeritinum from the Cicerae tribe, immediately basal to the Fabeae and Trifolieae tribes, suggested a single evolutionary origin of 4-Cl-IAA. Here, we provide a more robust phylogenetic placement of the ability to produce chlorinated auxin by screening key species spanning this evolutionary transition. We report no detectable level of 4-Cl-IAA in Cicer echinospermum (a wild relative of C. aeritinum) and 4 species (Galega officinalis, Parochetus communis, Astragalus propinquus and A. sinicus) from tribes or clades more basal or sister to the Cicerae tribe. We did detect 4-Cl-IAA in the dry seeds of 4 species from the genus Ononis that are either basal to the genera Medicago, Melilotus and Trigonella or basal to, but still within, the Fabeae and Trifolieae (ex. Parochetus) clades. We conclude that the single evolutionary origin of this hormone in seeds can be used as a phylogenetically informative trait within the Fabaceae. PMID:27302610

Unsupervised Gaussian Mixture-Model With Expectation Maximization for Detecting Glaucomatous Progression in Standard Automated Perimetry Visual Fields.

PubMed

Yousefi, Siamak; Balasubramanian, Madhusudhanan; Goldbaum, Michael H; Medeiros, Felipe A; Zangwill, Linda M; Weinreb, Robert N; Liebmann, Jeffrey M; Girkin, Christopher A; Bowd, Christopher

2016-05-01

To validate Gaussian mixture-model with expectation maximization (GEM) and variational Bayesian independent component analysis mixture-models (VIM) for detecting glaucomatous progression along visual field (VF) defect patterns (GEM-progression of patterns (POP) and VIM-POP). To compare GEM-POP and VIM-POP with other methods. GEM and VIM models separated cross-sectional abnormal VFs from 859 eyes and normal VFs from 1117 eyes into abnormal and normal clusters. Clusters were decomposed into independent axes. The confidence limit (CL) of stability was established for each axis with a set of 84 stable eyes. Sensitivity for detecting progression was assessed in a sample of 83 eyes with known progressive glaucomatous optic neuropathy (PGON). Eyes were classified as progressed if any defect pattern progressed beyond the CL of stability. Performance of GEM-POP and VIM-POP was compared to point-wise linear regression (PLR), permutation analysis of PLR (PoPLR), and linear regression (LR) of mean deviation (MD), and visual field index (VFI). Sensitivity and specificity for detecting glaucomatous VFs were 89.9% and 93.8%, respectively, for GEM and 93.0% and 97.0%, respectively, for VIM. Receiver operating characteristic (ROC) curve areas for classifying progressed eyes were 0.82 for VIM-POP, 0.86 for GEM-POP, 0.81 for PoPLR, 0.69 for LR of MD, and 0.76 for LR of VFI. GEM-POP was significantly more sensitive to PGON than PoPLR and linear regression of MD and VFI in our sample, while providing localized progression information. Detection of glaucomatous progression can be improved by assessing longitudinal changes in localized patterns of glaucomatous defect identified by unsupervised machine learning.

Determination of rutin and quercetin in Chinese herbal medicine by ionic liquid-based pressurized liquid extraction-liquid chromatography-chemiluminescence detection.

PubMed

Wu, Hongwei; Chen, Meilan; Fan, Yunchang; Elsebaei, Fawzi; Zhu, Yan

2012-01-15

A novel ionic liquid-based pressurized liquid extraction (IL-PLE) procedure coupled with high performance liquid chromatography (HPLC) tandem chemiluminescence (CL) detection capable of quantifying trace amounts of rutin and quercetin in four Chinese medicine plants including Flos sophorae Immaturus, Crateagus pinnatifida Bunge, Hypericum japonicum Thunb and Folium Mori was described in this paper. To avoid environmental pollution and toxicity to the operators, ionic liquids (ILs), 1-alkyl-3-methylimidazolium chloride ([C(n)mim][Cl]) aqueous solutions were used in the PLE procedure as extractants replacing traditional organic solvents. In addition, chemiluminescence detection was utilized for its minimal interference from endogenous components of complex matrix. Parameters affecting extraction and analysis were carefully optimized. Compared with the conventional ultrasonic-assisted extraction (UAE) and heat-reflux extraction (HRE), the optimized method achieved the highest extraction efficiency in the shortest extraction time with the least solvent consumption. The applicability of the proposed method to real sample was confirmed. Under the optimized conditions, good reproducibility of extraction performance was obtained and good linearity was observed with correlation coefficients (r) between 0.9997 and 0.9999. The detection limits of rutin and quercetin (LOD, S/N=3) were 1.1×10(-2)mg/L and 3.8×10(-3)mg/L, respectively. The average recoveries of rutin and quercetin for real samples were 93.7-105% with relative standard deviation (RSD) lower than 5.7%. To the best of our knowledge, this paper is the first contribution to utilize a combination of IL-PLE with chemiluminescence detection. And the experimental results indicated that the proposed method shows a promising prospect in extraction and determination of rutin and quercetin in medicinal plants. Copyright © 2011 Elsevier B.V. All rights reserved.

Waist-hip Ratio (WHR), a Better Predictor for Prostate Cancer than Body Mass Index (BMI): Results from a Chinese Hospital-based Biopsy Cohort.

PubMed

Tang, Bo; Han, Cheng-Tao; Zhang, Gui-Ming; Zhang, Cui-Zhu; Yang, Wei-Yi; Shen, Ying; Vidal, Adriana C; Freedland, Stephen J; Zhu, Yao; Ye, Ding-Wei

2017-03-08

To investigate whether waist-hip ratio (WHR) is a better predictor of prostate cancer (PCa) incidence than body mass index (BMI) in Chinese men. Of consecutive patients who underwent prostate biopsies in one tertiary center between 2013 and 2015, we examined data on 1018 with PSA ≤20 ng/ml. Clinical data and biopsy outcomes were collected. Logistic regression was used to evaluate the associations between BMI, WHR and PCa incidence. Area under the ROC (AUC) was used to evaluate the accuracy of different prognostic models. A total of 255 men and 103 men were diagnosed with PCa and high grade PCa (HGPCa, Gleason score ≥8). WHR was an independent risk factor for both PCa (OR = 1.07 95%Cl 1.03-1.11) and HGPCa (OR = 1.14 95%Cl 1.09-1.19) detection, while BMI had no relationship with either PCa or HGPCa detection. Adding WHR to a multivariable model increased the AUC for detecting HGPCa from 0.66 (95%Cl 0.60-0.72) to 0.71 (95%Cl 0.65-0.76). In this Chinese cohort, WHR was significantly predictive of PCa and HGPCa. Adding WHR to a multivariable model increased the diagnostic accuracy for detecting HGPCa. If confirmed, including WHR measurement may improve PCa and HGPCa detection.

Waist-hip Ratio (WHR), a Better Predictor for Prostate Cancer than Body Mass Index (BMI): Results from a Chinese Hospital-based Biopsy Cohort

PubMed Central

Tang, Bo; Han, Cheng-Tao; Zhang, Gui-Ming; Zhang, Cui-Zhu; Yang, Wei-Yi; Shen, Ying; Vidal, Adriana C.; Freedland, Stephen J.; Zhu, Yao; Ye, Ding-Wei

2017-01-01

To investigate whether waist-hip ratio (WHR) is a better predictor of prostate cancer (PCa) incidence than body mass index (BMI) in Chinese men. Of consecutive patients who underwent prostate biopsies in one tertiary center between 2013 and 2015, we examined data on 1018 with PSA ≤20 ng/ml. Clinical data and biopsy outcomes were collected. Logistic regression was used to evaluate the associations between BMI, WHR and PCa incidence. Area under the ROC (AUC) was used to evaluate the accuracy of different prognostic models. A total of 255 men and 103 men were diagnosed with PCa and high grade PCa (HGPCa, Gleason score ≥8). WHR was an independent risk factor for both PCa (OR = 1.07 95%Cl 1.03–1.11) and HGPCa (OR = 1.14 95%Cl 1.09–1.19) detection, while BMI had no relationship with either PCa or HGPCa detection. Adding WHR to a multivariable model increased the AUC for detecting HGPCa from 0.66 (95%Cl 0.60–0.72) to 0.71 (95%Cl 0.65–0.76). In this Chinese cohort, WHR was significantly predictive of PCa and HGPCa. Adding WHR to a multivariable model increased the diagnostic accuracy for detecting HGPCa. If confirmed, including WHR measurement may improve PCa and HGPCa detection. PMID:28272469

Detection of cephradine through the electrochemical study of the degradation product of cephradine

NASA Astrophysics Data System (ADS)

Jiang, Qingfeng; Ying, Yibin; Wang, Jianping; Ye, Zunzhong; Li, Yanbin

2005-11-01

The degradation product of cephradine(CEP), a broad spectrum antibiotic, with NaOH was studied in solution by Cyclic Voltammetry and Differential Pulse Voltammetry at a three electrode system (Gold working electrode, Hg/HgCl reference electrode and Platinum counter electrode). Our experiment was based on that the R-SH in degradation product could cause a deoxidization peak at gold working electrode. The response was optimized with respect to accumulation time, ionic strength, drug concentration, reproducibility and other variables. We found that the degradation product of CEP in Na2HPO4-NaH2PO4 buffer could cause a sensitive deoxidization peak at -0.68V. A linear dependence of peak currents on the concentration was observed in the range of 10-7 - 10-6 mol/L, with a detection limit of 0.5*10-7mol/L. This method can achieve satisfactory results in the application of detecting human-made CEP.

A competitive chemiluminescence enzyme immunoassay for rapid and sensitive determination of enrofloxacin

NASA Astrophysics Data System (ADS)

Yu, Fei; Wu, Yongjun; Yu, Songcheng; Zhang, Huili; Zhang, Hongquan; Qu, Lingbo; Harrington, Peter de B.

With alkaline phosphatase (ALP)-adamantane (AMPPD) system as the chemiluminescence (CL) detection system, a highly sensitive, specific and simple competitive chemiluminescence enzyme immunoassay (CLEIA) was developed for the measurement of enrofloxacin (ENR). The physicochemical parameters, such as the chemiluminescent assay mediums, the dilution buffer of ENR-McAb, the volume of dilution buffer, the monoclonal antibody concentration, the incubation time, and other relevant variables of the immunoassay have been optimized. Under the optimal conditions, the detection linear range of 350-1000 pg/mL and the detection limit of 0.24 ng/mL were provided by the proposed method. The relative standard deviations were less than 15% for both intra and inter-assay precision. This method has been successfully applied to determine ENR in spiked samples with the recovery of 103%-96%. It showed that CLEIA was a good potential method in the analysis of residues of veterinary drugs after treatment of related diseases.

Near-thermal reactions of Au(+)(1S,3D) with CH3X (X = F,Cl).

PubMed

Taylor, William S; Matthews, Cullen C; Hicks, Ashley J; Fancher, Kendall G; Chen, Li Chen

2012-01-26

Reactions of Au(+)((1)S) and Au(+)((3)D) with CH(3)F and CH(3)Cl have been carried out in a drift cell in He at a pressure of 3.5 Torr at both room temperature and reduced temperatures in order to explore the influence of the electronic state of the metal on reaction outcomes. State-specific product channels and overall two-body rate constants were identified using electronic state chromatography. These results indicate that Au(+)((1)S) reacts to yield an association product in addition to AuCH(2)(+) in parallel steps with both neutrals. Product distributions for association vs HX elimination were determined to be 79% association/21% HX elimination for X = F and 50% association/50% HX elimination when X = Cl. Reaction of Au(+)((3)D) with CH(3)F also results in HF elimination, which in this case is thought to produce (3)AuCH(2)(+). With CH(3)Cl, Au(+)((3)D) reacts to form AuCH(3)(+) and CH(3)Cl(+) in parallel steps. An additional product channel initiated by Au(+)((3)D) is also observed with both methyl halides, which yields CH(2)X(+) as a higher-order product. Kinetic measurements indicate that the reaction efficiency for both Au(+) states is significantly greater with CH(3)Cl than with CH(3)F. The observed two-body rate constant for depletion of Au(+)((1)S) by CH(3)F represents less than 5% of the limiting rate constant predicted by the average dipole orientation model (ADO) at room temperature and 226 K, whereas CH(3)Cl reacts with Au(+)((1)S) at the ADO limit at both room temperature and 218 K. Rate constants for depletion of Au(+)((3)D) by CH(3)F and CH(3)Cl were measured at 226 and 218 K respectively, and indicate that Au(+)((3)D) is consumed at approximately 2% of the ADO limit by CH(3)F and 69% of the ADO limit by CH(3)Cl. Product formation and overall efficiency for all four reactions are consistent with previous experimental results and available theoretical models.

Selective detection and recovery of gold at tannin-immobilized non-conducting electrode.

PubMed

Banu, Khaleda; Shimura, Takayoshi; Sadeghi, Saman

2015-01-01

A tannin-immobilized glassy carbon electrode (TIGC) was prepared via electrochemical oxidation of the naturally occurring polyphenolic mimosa tannin, which generated a non-conducting polymeric film (NCPF) on the electrode surface. The fouling of the electrode surface by the electropolymerized film was evaluated by monitoring the electrode response of ferricyanide ions as a redox marker. The NCPF was permselective to HAuCl4, and the electrochemical reduction of HAuCl4 to metallic gold at the TIGC electrode was evaluated by recording the reduction current during cyclic voltammetry measurement. In the mixed electrolyte containing HAuCl4 along with FeCl3 and/or CuCl2, the NCPF remained selective toward the electrochemical reduction of HAuCl4 into the metallic state. The chemical reduction of HAuCl4 into metallic gold was also observed when the NCPF was inserted into an acidic gold solution overnight. The adsorption capacity of Au(III) on tannin-immobilized carbon fiber was 29±1.45 mg g(-1) at 60°C. In the presence of excess Cu(II) and Fe(III), tannin-immobilized NCPF proved to be an excellent candidate for the selective detection and recovery of gold through both electrochemical and chemical processes. Copyright © 2014 Elsevier B.V. All rights reserved.

A single use electrochemical sensor based on biomimetic nanoceria for the detection of wine antioxidants.

PubMed

Andrei, Veronica; Sharpe, Erica; Vasilescu, Alina; Andreescu, Silvana

2016-08-15

We report the development and characterization of a disposable single use electrochemical sensor based on the oxidase-like activity of nanoceria particles for the detection of phenolic antioxidants. The use of nanoceria in the sensor design enables oxidation of phenolic compounds, particularly those with ortho-dihydroxybenzene functionality, to their corresponding quinones at the surface of a screen printed carbon electrode. Detection is carried out by electrochemical reduction of the resulting quinone at a low applied potential of -0.1V vs the Ag/AgCl electrode. The sensor was optimized and characterized with respect to particle loading, applied potential, response time, detection limit, linear concentration range and sensitivity. The method enabled rapid detection of common phenolic antioxidants including caffeic acid, gallic acid and quercetin in the µM concentration range, and demonstrated good functionality for the analysis of antioxidant content in several wine samples. The intrinsic oxidase-like activity of nanoceria shows promise as a robust tool for sensitive and cost effective analysis of antioxidants using electrochemical detection. Copyright © 2016 Elsevier B.V. All rights reserved.

Atacama perchlorate as an agricultural contaminant in groundwater: Isotopic and chronologic evidence from Long Island, New York

USGS Publications Warehouse

Böhlke, J.K.; Hatzinger, P.B.; Sturchio, N.C.; Gu, B.; Abbene, I.; Mroczkowski, S.J.

2009-01-01

Perchlorate (ClO4-) is a common groundwater constituent with both synthetic and natural sources. A potentially important source of ClO4- is past agricultural application of ClO4--bearing natural NO3- fertilizer imported from the Atacama Desert, Chile, but evidence for this hasbeenlargely circumstantial. Here we report ClO4- stable isotope data (??37Cl, ??18O, and ??17O), along with other supporting chemical and isotopic environmental tracer data, to document groundwater ClO4- contamination sources and history in parts of Long Island, New York. Sampled groundwaters were oxic and ClO4- apparently was not affected by biodegradation within the aquifers. Synthetic ClO4- was indicated by the isotopic method in groundwater near a fireworks disposal site at a former missile base. Atacama ClO4- was indicated in agricultural and urbanizing areas in groundwaters with apparent ages >20 years. In an agricultural area, ClO4- concentrations and ClO4-/NO3- ratios increased withgroundwaterage, possiblybecauseof decreasing application rates of Atacama NO3- fertilizers and/or decreasing ClO4- concentrations in Atacama NO 3- fertilizers in recent years. Because ClO 4-/NO3- ratios of Atacama NO 3- fertilizers imported in the past (???2 ?? 10-3 mol mol-1) were much higher than the ClO 4-/NO3- ratio of recommended drinking-water limits (7 ?? 10-5 mol mol-1 in New York), ClO4- could exceed drinkingwater limits even where NO3- does not, and where Atacama NO3- was only a minor source of N. Groundwater ClO4- with distinctive isotopic composition was a sensitive indicator of past Atacama NO3- fertilizer use on Long Island and may be common in other areas that received NO3- fertilizers from the late 19th century through the 20th century. ?? 2009 American Chemical Society.

SERS activity with tenfold detection limit optimization on a type of nanoporous AAO-based complex multilayer substrate

NASA Astrophysics Data System (ADS)

Sui, Chaofan; Wang, Kaige; Wang, Shuang; Ren, Junying; Bai, Xiaohong; Bai, Jintao

2016-03-01

Most of SERS applications are constricted by heterogeneous hotspots and aggregates of nanostructure, which result in low sensitivity and poor reproducibility of characteristic signals. This work intends to introduce SERS properties of a type of SERS-active substrate, Au-CuCl2-AAO, which is innovatively developed on a porous anodic alumina oxide (AAO) template. Spectral measuring results of Rhodamine 6G (R6G) on this substrate optimized by controlling morphology and gold thickness showed that enhancement factor (2.30 × 107) and detection limit (10-10 M) were both improved and represented better performance than its template AAO. Homogenous hot spots across the region of interest were achieved by scanning SERS intensity distribution for the band at 1505 cm-1 in 5 × 5 μm2 area. Furthermore, the promising SERS activity of the flower-patterned substrate was theoretically explained through simulation of the electromagnetic field distribution. In addition, this SERS substrate is proposed for applications within the field of chemical and biochemical analyses.Most of SERS applications are constricted by heterogeneous hotspots and aggregates of nanostructure, which result in low sensitivity and poor reproducibility of characteristic signals. This work intends to introduce SERS properties of a type of SERS-active substrate, Au-CuCl2-AAO, which is innovatively developed on a porous anodic alumina oxide (AAO) template. Spectral measuring results of Rhodamine 6G (R6G) on this substrate optimized by controlling morphology and gold thickness showed that enhancement factor (2.30 × 107) and detection limit (10-10 M) were both improved and represented better performance than its template AAO. Homogenous hot spots across the region of interest were achieved by scanning SERS intensity distribution for the band at 1505 cm-1 in 5 × 5 μm2 area. Furthermore, the promising SERS activity of the flower-patterned substrate was theoretically explained through simulation of the electromagnetic field distribution. In addition, this SERS substrate is proposed for applications within the field of chemical and biochemical analyses. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06771e

On the use of L-012, a luminol-based chemiluminescent probe, for detecting superoxide and identifying inhibitors of NADPH oxidase: A re-evaluation

PubMed Central

Zielonka, Jacek; Lambeth, J. David; Kalyanaraman, Balaraman

2014-01-01

L-012, a luminol-based chemiluminescent (CL) probe, is widely used in vitro and in vivo to detect NADPH oxidase (Nox)-derived superoxide (O2·−) and identify Nox inhibitors. Yet understanding of the free radical chemistry of L-012 probe is still lacking. We report that peroxidase and H2O2 induce superoxide dismutase (SOD)-sensitive, L-012-derived CL in the presence of oxygen. O2·− alone does not react with L-012 to emit luminescence. Self-generated O2·− during oxidation of L-012 and luminol-analogs artifactually induce CL inhibitable by SOD. These aspects make assays based on luminol analogs less than ideal for specific detection and identification of O2·− and NOX inhibitors. PMID:24080119

Kinetics and Thermochemistry of Reversible Adduct Formation in the Reaction of Cl((sup 2)P(sub J)) with CS2

NASA Technical Reports Server (NTRS)

Nicovich, J. M.; Shackelford, C. J.; Wine, P. H.

1997-01-01

Reversible adduct formation in the reaction of Cl((sup 2)P(sub J)) with CS2 has been observed over the temperature range 193-258 K by use of time-resolved resonance fluorescence spectroscopy to follow the decay of pulsed-laser-generated Cl((sup 2)P(sub J)) into equilbrium with CS2Cl. Rate coefficients for CS2Cl formation and decomposition have been determined as a function of temperature and pressure; hence, the equilbrium constant has been determined as a function of temperature. A second-law analysis of the temperature dependence of Kp and heat capacity corrections calculated with use of an assumed CS2Cl structure yields the following thermodynamic parameters for the association reaction: Delta-H(sub 298) = -10.5 +/- 0.5 kcal/mol, Delta-H(sub 0) = -9.5 +/- 0.7 kcal/mol, Delta-S(sub 298) = -26.8 +/- 2.4 cal/mol.deg., and Delta-H(sub f,298)(CS2Cl) = 46.4 +/- 0.6 kcal/mol. The resonance fluorescence detection scheme has been adapted to allow detection of Cl((sup 2)P(sub J)) in the presence of large concentrations of O2, thus allowing the CS2Cl + Cl + O2 reaction to be investigated. We find that the rate coefficient for CS2Cl + O2 reaction via all channels that do not generate Cl((sup 2)P(sub J)) is less than 2.5 x 10(exp-16) cu cm/(molecule.s) at 293 K and 300-Torr total pressure and that the total rate coefficient is less than 2 x 10 (exp -15) cu cm/(molecule.s) at 230 K and 30-Torr total pressure. Evidence for reversible adduct formation in the reaction of Cl((sup 2)P(sub J)) with COS was sought but not observed, even at temperatures as low as 194 K.

LASER RADIATION CHARACTERISTICS (BRIEF COMMUNICATIONS): Conversion of KrCl and XeCl laser radiation to the visible spectral range by stimulated Raman scattering in lead vapor

NASA Astrophysics Data System (ADS)

Evtushenko, Gennadii S.; Mel'chenko, S. V.; Panchenko, Aleksei N.; Tarasenko, Viktor F.

1990-04-01

Conversion of KrCl and XeCl laser radiation by stimulated Raman scattering was achieved in lead vapor. The KrCl laser radiation was converted into three lines in the visible region at λ = 406, 590, and 723 nm by transitions from both the ground and first excited levels of the lead atom. The conversion efficiency of XeCl laser radiation of low spatial coherence was found to be limited by the activation of a competing nonlinear process.

Covalent organic framework as efficient desorption/ionization matrix for direct detection of small molecules by laser desorption/ionization mass spectrometry.

PubMed

Feng, Dan; Xia, Yan

2018-07-19

Covalent organic framework (COF) was explored as a novel matrix with a high desorption/ionization efficiency for direct detection of small molecules by laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF MS). By using COF as an LDI MS matrix, we could detect not only biological micro molecules such as amino acids and fatty acids, but also emerging environmental pollutants like bisphenol S (BPS) and pyrene. With COF as the matrix, higher desorption/ionization efficiency, and less background interference were achieved than the conventional organic matrices. Good salt tolerance (as high as 500 mM NaCl) and repeatability allowed the detection limit of amino acids was 90 fmol. In addition, COF matrix performed well for amino acids analysis in the honey sample. The ionization mechanism was also discussed. These results demonstrate that COF is a powerful matrix for small molecules analysis in real samples by MS. Copyright © 2018 Elsevier B.V. All rights reserved.

First measurements of the new ClO-mm-wave sounder at the Jungfraujoch Alpine Station

NASA Technical Reports Server (NTRS)

Gerber, Louis; Kaempfer, Niklaus

1994-01-01

In the last years much progress has been made in the field of the detection of stratospheric trace constituents. However, only few techniques are suitable to detect ClO, one of the key constituents in ozone depletion chemistry. One of these techniques is mm-wave radiometry. This work presents the first measurements performed by a new 204 GHz radiometer at the Jungfraujoch Alpine Station.

Development and validation of the first assay method coupling liquid chromatography with chemiluminescence for the simultaneous determination of menadione and its thioether conjugates in rat plasma.

PubMed

Elgawish, Mohamed Saleh; Shimomai, Chikako; Kishikawa, Naoya; Ohyama, Kaname; Wada, Mitsuhiro; Kuroda, Naotaka

2013-09-16

Menadione (2-methyl-1,4-naphthoquinone, MQ), a component of multivitamin drugs with antihemorrhagic, antineoplastic, and antimalarial activity, is frequently used to investigate quinone-induced cytotoxicity. The formation of MQ conjugates with glutathione (GSH) by Michael addition and subsequent biotransformation to yield N-acetyl-l-cysteine conjugates is believed to be an important detoxification process. However, the resulting conjugates, 2-methyl-3-(glutathione-S-yl)-1,4-naphthoquinone (MQ-GS) and 2-methyl-3-(N-acetyl-l-cysteine-S-yl)-1,4-naphthoquinone (MQ-NAC), retain the ability to redox cycle and to arylate cellular nucleophiles. Although the nephrotoxicity and hepatotoxicity of MQ-thiol conjugates have been reported in vitro, methods for their determination in vivo have yet to be published. Herein, a highly sensitive, simple, and selective HPLC-chemiluminescence (HPLC-CL) coupled method is reported, allowing for the first time the simultaneous determination of MQ, MQ-GS, and MQ-NAC in rat plasma after MQ administration. Our method exploits the unique redox characteristics of MQ, MQ-GS, and MQ-NAC to react with dithiothreitol (DTT) to liberate reactive oxygen species (ROS) which are detected by a CL assay using luminol as a CL probe. To verify the proposed mechanism, MQ-GS and MQ-NAC were synthetically prepared. Specimen preparation involved solid-phase extraction on an Oasis HLB cartridge followed by isocratic elution on an ODS column. No interference from endogenous substances was detected. Linearity was observed in the range of 5-120 nM for MQ-GS and MQ-NAC and 10-240 nM for MQ, with detection limits (S/N of 3) of 1.4, 0.8, and 128 fmol for MQ-GS, MQ-NAC, and MQ, respectively. The application of our method reported here is the first to extensively study the stability and reversibility of thiol-quinones.

Plasma-membrane H(+)-ATPase gene expression is regulated by NaCl in cells of the halophyte Atriplex nummularia L.

PubMed

Niu, X; Zhu, J K; Narasimhan, M L; Bressan, R A; Hasegawa, P M

1993-01-01

An Atriplex nummularia L. cDNA probe encoding the partial sequence of an isoform of the plasma-membrane H(+)-ATPase was isolated, and used to characterize the NaCl regulation of mRNA accumulation in cultured cells of this halophyte. The peptide (477 amino acids) translated from the open reading frame has the highest sequence homology to the Nicotiana plumbaginifolia plasma-membrane H(+)-ATPase isoform pma4 (greater than 80% identity) and detected a transcript of approximately 3.7 kb on Northern blots of both total and poly(A)+ RNA. The mRNA levels were comparable in unadapted cells, adapted cells (cells adapted to and growing in 342 mM NaCl) and deadapted cells (cells previously adapted to 342 mM NaCl that are now growing without salt). Increased mRNA abundance was detected in deadapted cells within 24 h after exposure to NaCl but not in unadapted cells with similar salt treatments. The NaCl up-regulation of message abundance in deadapted cells was subject to developmental control. Analogous to those reported for glycophytes, the plasma-membrane H(+)-ATPase are encoded by a multigene family in the halophyte.

RNA sequencing analysis of transcriptional change in the freshwater mussel Elliptio complanata after environmentally relevant sodium chloride exposure

USGS Publications Warehouse

Robertson, Laura S.; Galbraith, Heather S.; Iwanowicz, Deborah; Blakeslee, Carrie J.; Cornman, Robert S.

2017-01-01

To identify potential biomarkers of salt stress in a freshwater sentinel species, we examined transcriptional responses of the common mussel Elliptio complanata to controlled sodium chloride (NaCl) exposures. Ribonucleic acid sequencing (RNA-Seq) of mantle tissue identified 481 transcripts differentially expressed in adult mussels exposed to 2 ppt NaCl (1.2 ppt chloride) for 7 d, of which 290 had nonoverlapping intervals. Differentially expressed gene categories included ion and transmembrane transport, oxidoreductase activity, maintenance of protein folding, and amino acid metabolism. The rate-limiting enzyme for synthesis of taurine, an amino acid frequently linked to osmotic stress in aquatic species, was upregulated, as was the transmembrane ion pump sodium/potassium adenosine 5′-triphosphatase. These patterns confirm a primary transcriptional response to the experimental dose, albeit likely overlapping with nonspecific secondary stress responses. Substantial involvement of the heat shock protein 70 chaperone family and the water-transporting aquaporin family was not detected, however, in contrast to some studies in other bivalves. A subset of the most significantly regulated genes was confirmed by quantitative polymerase chain reaction in an independent sample. Cluster analysis showed separation of mussels exposed to 2 ppt NaCl from control mussels in multivariate space, but mussels exposed to 1 ppt NaCl were largely indistinguishable from controls. Transcriptome-scale analysis of salt exposure under laboratory conditions efficiently identified candidate biomarkers for further functional analysis and field validation

Electrochemical Study of Carbon Nanotubes/Nanohybrids for Determination of Metal Species Cu2+ and Pb2+ in Water Samples

PubMed Central

Oliveira Silva, Andréa Claudia; de Oliveira, Luis Carlos Ferreira; Vieira Delfino, Angladis; Meneghetti, Mario Roberto

2016-01-01

The use of nanomaterials, such as nanoparticles and nanotubes, for electrochemical detection of metal species has been investigated as a way of modifying electrodes by electrochemical stripping analysis. The present study develops a new methodology based on a comparative study of nanoparticles and nanotubes with differential pulse anodic stripping voltammetry (DPASV) and examines the simultaneous determination of copper and lead. The glassy carbon electrode modified by gold nanoparticles demonstrated increased sensitivity and decreased detection limits, among other improvements in analytical performance data. Under optimized conditions (deposition potential −0.8 V versus Ag/AgCl; deposition time, 300 s; resting time, 10 s; pulse amplitude, 50 mV; and voltage step height, 4 mV), the detection limits were 0.2279 and 0.3321 ppb, respectively, for determination of Pb2+ and Cu2+. The effects of cations and anions on the simultaneous determination of metal ions do not exhibit significant interference, thereby demonstrating the selectivity of the electrode for simultaneous determination of Pb2+ and Cu2+. The same method was also used to determine Cu2+ in water samples. PMID:27882263

Determination of trace-level haloacetic acids in drinking water by ion chromatography-inductively coupled plasma mass spectrometry.

PubMed

Liu, Yongjian; Mou, Shifen; Chen, Dengyun

2004-06-11

A new method for the determination of nine haloacetic acids (HAAs) with ion chromatography (IC) coupled to inductively coupled plasma mass spectrometry (ICP-MS) was developed. With the very hydrophilic anion-exchange column and steep gradient of sodium hydroxide, the nine HAAs could be well separated in 15 min. After suppression with an ASRS suppressor that was introduced in between IC and ICP-MS, the background was much decreased, the interference caused by sodium ion present in eluent was removed, and the sensitivities of HAAs were greatly improved. The chlorinated and brominated HAAs could be detected as 35ClO and 79Br without interference of the matrix due to the elemental selective ICP-MS. The detection limits for mono-, di-, trichloroacetic acids were between 15.6 and 23.6 microg/l. For the other six bromine-containing HAAs, the detection limits were between 0.34 and 0.99 microg/l. With the pretreatment of OnGuard Ag cartridge to remove high concentration of chloride in sample, the developed method could be applied to the determination of HAAs in many drinking water matrices.

A colorimetric and fluorometric dual-signal sensor for arginine detection by inhibiting the growth of gold nanoparticles/carbon quantum dots composite.

PubMed

Liu, Ting; Li, Na; Dong, Jiang Xue; Zhang, Ying; Fan, Yu Zhu; Lin, Shu Min; Luo, Hong Qun; Li, Nian Bing

2017-01-15

A bidimensional optical sensing platform which combines the advantages of fluorescence and colorimetry has been designed for arginine (Arg) detection. The system was established by monitoring the influence of Arg on the growth of gold nanoparticles/carbon quantum dots (Au/CQDs) composite, and the CQDs synthesized by ethylene glycol were used as the reducing and stabilizing agent in this paper. Considering that Arg is the only amino acid with guanidine group and has the highest isoelectric point (pI) value at 10.76, Arg would carry positive charges at pH 7.4. Consequently, the positively charged guanidine group of Arg could attract AuCl 4 - and CQDs through electrostatic interaction, which inhibited the growth of Au/CQDs composite. Thereby, the color of the system almost did not change and the fluorescence quenching of CQDs was prevented in the presence of Arg. Based on the color change a low detection limit for Arg was 37nM, and a detection limit of 450nM was obtained by fluorescence spectroscopy. Moreover, this dual-signal sensor also revealed excellent selectivity toward Arg over other amino acids. Besides, Arg can be detected in urine samples with satisfactory results, which demonstrate the potential applications for real analysis. Copyright © 2016 Elsevier B.V. All rights reserved.

A glassy carbon electrode modified with poly(2,4-dinitrophenylhydrazine) for simultaneous detection of dihydroxybenzene isomers.

PubMed

Lopa, Nasrin Siraj; Rahman, Md Mahbubur; Jang, Hohyoun; Sutradhar, Sabuj Chandra; Ahmed, Faiz; Ryu, Taewook; Kim, Whangi

2017-12-06

2,4-Dinitrophenylhydrazine (DNPH) was electropolymerized on the surface of an anodized glassy carbon electrode by cyclic voltammetry. The anodized electrode has a highly electroactive surface due to the creation of chemically functionalized graphitic nanoparticles, and this facilitates the formation of poly-DNPH via radical polymerization. Poly-DNPH displays excellent redox activity due to the presence of nitro groups on its backbone. These catalyze the electro-oxidation of hydroquinone (HQ) and catechol (CT). The peak-to-peak separation is around 109 mV, while a bare GCE cannot resolve the peaks (located at 165 and 274 mV vs. Ag/AgCl). Sensitivity is also enhanced to ∼1.20 and 1.19 μA·cm -2 ·μM -1 , respectively. The sensor has a linear response that covers the 20-250 μM concentration range for both HQ and CT, with 0.75 and 0.76 μM detection limits, respectively, at simultaneous detection. Commonly present species do not interfere. Graphical abstract A novel conducting poly(2,4-dinitrophenylhydrazine)-modified anodized glassy carbon electrode (pDNPH/AGCE) was developed by electrochemical method. The electro-catalytic activity of pDNPH/AGCE sensor was investigated for the selective and simultaneous electrochemical detection of hydroquinone (HQ) and catechol (CT), which revealed high sensitivities and low detection limits with excellent stability.

Occurrence and seasonal variations of per- and polyfluoroalkyl substances (PFASs) including fluorinated alternatives in rivers, drain outlets and the receiving Bohai Sea of China.

PubMed

Chen, Hong; Han, Jianbo; Zhang, Can; Cheng, Jiayi; Sun, Ruijun; Wang, Xiaomeng; Han, Gengchen; Yang, Wenchao; He, Xin

2017-12-01

A simultaneous sampling campaign was undertaken to study the pollution by 21 per- and polyfluoroalkyl substances (PFASs) in rivers, drain outlets and their receiving Bohai Sea of China. Chlorinated polyfluoroalkyl ether sulfonic acids (Cl-PFESAs) are being used as fluorinated alternatives and they were included in this study. In comparison with other regions and countries, high concentrations of ∑ 21 PFASs in seawater samples from the Bohai Sea, ranging from 5.03 to 41 700 ng/L (median: 64.8 ng/L), were observed. The spatial distribution of PFAS levels in this sea area was in the ranking of Laizhou Bay > Liaodong Bay > Bohai Bay > other sea areas. By comparing the levels and composition profiles of PFASs in the seawater and their sources (rivers and drain outlets), it was concluded that rivers and drain outlets are the primary sources of PFAS contamination to the Bohai Sea. These PFAS levels varied seasonally among the rivers and drain outlets, but statistically significant changes were not observed. Levels of 6:2 and 8:2 Cl-PFESAs in rivers, drain outlets and receiving sea were firstly reported in the present study. Relatively high concentrations of 6:2 Cl-PFESA were found in drain outlets, ranging from below method limits of quantification (MLQ) to 7600 ng/L, but 8:2 Cl-PFAES detection was infrequent and all median concentration below MLQ. Mass discharges to the sea of 6:2 Cl-PFESA from rivers and drain outlets to the sea were estimated to be 37 and 17 kg/y, respectively. Copyright © 2017. Published by Elsevier Ltd.

Development and application of GC-MS method for monitoring of long-term exposure to the pesticide cypermethrin.

PubMed

Kavvalakis, Matthaios P; Tzatzarakis, Manolis N; Alegakis, Athanasios K; Vynias, Dionysios; Tsakalof, Andreas K; Tsatsakis, Aristidis M

2014-06-01

Cypermethrin (CPMN) is a synthetic pyrethroid used as an insecticide in large-scale commercial agricultural applications as well as for domestic purposes. In the present study a gas chromatography-mass spectrometry (GC-MS) based method was developed and validated for the quantitation of CPMN metabolites, 3-phenoxybenzoic acid (3-PBA) and cis- and trans- 3-(2,2-dichlorovinyl)-2,2-dimethyl-1-cyclopropane (cis- and trans- Cl2 CA). The developed method was applied for the monitoring of CPMN metabolites in hair of laboratory animals (rabbits) intentionally exposed per os to CPMN at 40 (low dose) and 80 (high dose) mg/kg weight/day for 16 weeks. The analytical method comprises three main steps: isolation of analytes from hair, analytes derivatization, and subsequent instrumental analysis by GC-MS. The limits of detection ensured by the method are 4.0, 3.9 and 1.0 pg/mg hair for cis-Cl2 CA, trans-Cl2 CA and 3-PBA, respectively. The instrument responce is linear (r(2)  > 0.99) in the investigated concentrations range from 25 to 1000 pg/mg. With and between-run precision as well as accuracy were estimated and found satisfactory. Analytes were efficiently isolated by solid-liquid extraction from hair with recoveries greater than 84.8% for cis-Cl2 CA, 87.2% for trans-Cl2 CA and 96.4% for 3-PBA. Rabbit's hair showed increasing levels for all metabolites (metabolites accumulation in a time and dose dependent manner) over time and in a dose-dependent manner. The developed experimental procedure could be used for biomonitoring of population exposure to CPMN. Copyright © 2014 John Wiley & Sons, Ltd.

Molecular Epidemiological Survey of Cutaneous Leishmaniasis in Two Highly Endemic Metropolises of Iran, Application of FTA Cards for DNA Extraction From Giemsa-Stained Slides.

PubMed

Izadi, Shahrokh; Mirhendi, Hossein; Jalalizand, Niloufar; Khodadadi, Hossein; Mohebali, Mehdi; Nekoeian, Shahram; Jamshidi, Ali; Ghatee, Mohammad Amin

2016-02-01

PCR has been used for confirmation of leishmaniasis in epidemiological studies, but complexity of DNA extraction and PCR approach has confined its routine use in developing countries. In this study, recent epidemiological situation of cutaneous leishmaniasis (CL) in two hyper-endemic metropolises of Shiraz and Isfahan in Iran was studied using DNA extraction by commercial FTA cards and kinetoplastid DNA (kDNA)-PCR amplification for detection/identification of Leishmania directly from stained skin scraping imprints. Fifty four and 30 samples were collected from clinically diagnosed CL patients referred to clinical laboratories of leishmaniasis control centers in Isfahan and Shiraz cities, respectively. The samples were examined by direct microscopy and then scrapings of the stained smears were applied to FTA cards and used directly as DNA source in a nested-PCR to amplify kDNA to detect and identify Leishmania species. Fifty four of 84 (64.2%) slides obtained from patients had positive results microscopically, while 79/84 (94%) of slides had positive results by FTA card-nested-PCR. PCR and microscopy showed a sensitivity of 96.4% and 64.2% and specificity of 100% and 100%, respectively. Interestingly, Leishmania major as causative agent of zoonotic CL was identified in 100% and 90.7% of CL cases from Isfahan and Shiraz cities, respectively, but L. tropica was detected from only 9.3% of cases from Shiraz city. All cases from central regions of Shiraz were L. tropica and no CL case was found in Isfahan central areas. Filter paper-based DNA extraction can facilitate routine use of PCR for diagnosis of CL in research and diagnostic laboratories in Iran and countries with similar conditions. Epidemiologic changes including dominancy of L. major in suburbs of Shiraz and Isfahan metropolises where anthroponotic CL caused by L. tropica had been established, showed necessity of precise studies on CL epidemiology in old urban and newly added districts in the suburbs.

Simultaneous determination of gabapentin, pregabalin, vigabatrin, and topiramate in plasma by HPLC with fluorescence detection.

PubMed

Martinc, Boštjan; Roškar, Robert; Grabnar, Iztok; Vovk, Tomaž

2014-07-01

Therapeutic drug monitoring (TDM) of antiepileptic drugs (AEDs) has been recognized as a useful tool in management of epilepsy. We developed a simple analytical method for simultaneous determination of four second generation AEDs, including gabapentin (GBP), pregabalin (PGB), vigabatrin (VGB), and topiramate (TOP). Analytes were extracted from human plasma using universal solid phase extraction, derivatized with 4-chloro-7-nitrobenzofurazan (NBD-Cl) and analyzed by HPLC with fluorescence detection. Using mass spectrometry we confirmed that NBD-Cl reacts with sulfamate group of TOP similarly as with amine group of the other three analytes. The method is linear (r(2)>0.998) across investigated analytical ranges (0.375-30.0μg/mL for GBP, PGB, and VGB; 0.50-20.0μg/mL for TOP). Intraday and interday precision do not exceed 9.40%. The accuracy is from 95.6% to 106%. The recovery is higher than 80.6%, and the lower limit of quantification is at least 0.5μg/mL. The method is selective and robust. For TOP determination the method was compared to a previously published method and the results obtained by the two methods were in good agreement. The developed method is suitable for routine TDM. Copyright © 2014 Elsevier B.V. All rights reserved.

Amorphous carbon nanoparticle used as novel resonance energy transfer acceptor for chemiluminescent immunoassay of transferrin.

PubMed

Gao, Hongfei; Wang, Wenwen; Wang, Zhenxing; Han, Jing; Fu, Zhifeng

2014-03-28

Amorphous carbon nanoparticles (ACNPs) showing highly efficient quenching of chemiluminescence (CL) were prepared from candle soot with a very simple protocol. The prepared ACNP was employed as the novel energy acceptor for a chemiluminescence resonance energy transfer (CRET)-based immunoassay. In this work, ACNP was linked with transferrin (TRF), and horseradish peroxidase (HRP) was conjugated to TRF antibody (HRP-anti-TRF). The immunoreaction rendered the distance between the ACNP acceptor and the HRP-catalyzed CL emitter to be short enough for CRET occurring. In the presence of TRF, this antigen competed with ACNP-TRF for HRP-anti-TRF, thus led to the decreased occurrence of CRET. A linear range of 20-400 ng mL(-1) and a limit of detection of 20 ng mL(-1) were obtained in this immunoassay. The proposed method was successfully applied for detection of TRF levels in human sera, and the results were in good agreement with ELISA method. Moreover, the ACNPs show higher energy transfer efficiency than other conventional nano-scaled energy acceptors such as graphene oxide in CRET assay. It is anticipated that this approach can be developed for determination of other analytes with low cost, simple manipulation and high specificity. Copyright © 2014 Elsevier Ltd. All rights reserved.

Electrochemical inactivation kinetics of boron-doped diamond electrode on waterborne pathogens.

PubMed

Yao, Yanyan; Kubota, Yoshinobu; Murakami, Taketoshi; Ochiai, Tsuyoshi; Ishiguro, Hitoshi; Nakata, Kazuya; Fujishima, Akira

2011-09-01

A boron-doped diamond (BDD) electrode was constructed as a water disinfector for the inactivation of water borne pathogens. The bactericidal effect of the disinfector was evaluated on artificially contaminated waters containing, respectively, Escherichia coli, Pseudomonas aeruginosa and Legionella pneumophila at high density. By treating the bacterial suspensions with 4 V of constant voltage between the BDD and the counter-electrode for 50 min, the population of E. coli and P. aeruginosa decreased from (10E + 7-8 colony-forming unit mL(-1)) to below the detection limits of the colony-formation method. Meanwhile, L. pneumophila were reduced to virtually zero when analyzed by fluorescence-based staining. The influences of production parameters (voltage, NaCl concentration and flow rate) on the disinfection kinetics of the BDD disinfector were examined with respect to operational conditions. Voltage was the most significant factor for adjusting the extent of electrolysis, followed by NaCl concentration and flow rate, to influence the disinfection efficiency. The disinfection of natural river water samples containing numerous microbes was performed for a practicability investigation of the BDD electrode. Approximately 99.99% bactericidal efficiency was confirmed by viability detection for E. coli and common germs in treated water. The results showed that the BDD electrode is a promising tool for various wastewater disinfections to combat waterborne diseases.

Simultaneous determination of isoniazid and p-aminosalicylic acid by capillary electrophoresis using chemiluminescence detection.

PubMed

Zhang, Xinfeng; Xuan, Yuelan; Sun, Aimin; Lv, Yi; Hou, Xiandeng

2009-01-01

It was found that isoniazid (ISO) or p-aminosalicylic acid (PAS) could enhance the chemiluminescence (CL) emission from Cu (II)-luminol-hydrogen peroxide system, and the increased chemiluminescence signals were proportional to their concentrations, respectively. Based on this phenomenon, a chemiluminescence method coupled to capillary electrophoresis (CE) was established for simultaneous determination of ISO and PAS. The CE conditions including running buffer and running voltage were investigated in detail. The effects of the pH of H(2)O(2) solution and the concentrations of luminol, H(2)O(2) and Cu (II) on the CL signal were also investigated carefully. Under the optimized conditions, the analysis could be accomplished within 10 min, with the limits of detection of 0.3 microg mL(-1) for ISO and 1.1 microg mL(-1) for PAS, corresponding to 7.2 and 26.4 pg per injection (24 nL), respectively. Finally, the method was validated by determining the two analytes in pharmaceutical preparation and spiked human serum samples. The results of pharmaceutical tablet analysis were in good agreement with the labeled amounts. The recoveries for ISO and PAS in human serum were in the range of 92-104% and 90-113%, respectively. Copyright 2008 John Wiley & Sons, Ltd.

Generation and detection of metal ions and volatile organic compounds (VOCs) emissions from the pretreatment processes for recycling spent lithium-ion batteries.

PubMed

Li, Jia; Wang, Guangxu; Xu, Zhenming

2016-06-01

The recycling of spent lithium-ion batteries brings benefits to both economic and environmental terms, but it can also lead to contaminants in a workshop environment. This study focused on metals, non-metals and volatile organic compounds generated by the discharging and dismantling pretreatment processes which are prerequisite for recycling spent lithium-ion batteries. After discharging in NaCl solution, metal contents in supernate and concentrated liquor were detected. Among results of condition #2, #3, #4 and #5, supernate and concentrated liquor contain high levels of Na, Al, Fe; middle levels of Co, Li, Cu, Ca, Zn; and low levels of Mn, Sn, Cr, Zn, Ba, K, Mg, V. The Hg, Ag, Cr and V are not detected in any of the analyzed supernate. 10wt% NaCl solution was a better discharging condition for high discharge efficiency, less possible harm to environment. To collect the gas released from dismantled LIB belts, a set of gas collecting system devices was designed independently. Two predominant organic vapour compounds were dimethyl carbonate (4.298mgh(-1)) and tert-amylbenzene (0.749mgh(-1)) from one dismantled battery cell. To make sure the concentrations of dimethyl carbonate under recommended industrial exposure limit (REL) of 100mgL(-1), for a workshop on dismantling capacity of 1000kg spent LIBs, the minimum flow rate of ventilating pump should be 235.16m(3)h(-1). Copyright © 2016 Elsevier Ltd. All rights reserved.

Electrochemical sensor based on gold nanoparticles fabricated molecularly imprinted polymer film at chitosan-platinum nanoparticles/graphene-gold nanoparticles double nanocomposites modified electrode for detection of erythromycin.

PubMed

Lian, Wenjing; Liu, Su; Yu, Jinghua; Xing, Xianrong; Li, Jie; Cui, Min; Huang, Jiadong

2012-01-01

A molecularly imprinted electrochemical sensor was fabricated based on gold electrode decorated by chitosan-platinum nanoparticles (CS-PtNPs) and graphene-gold nanoparticles (GR-AuNPs) nanocomposites for convenient and sensitive determination of erythromycin. The synergistic effects of CS-PtNPs and GR-AuNPs nanocomposites improved the electrochemical response and the sensitivity of the sensor. The molecularly imprinted polymers (MIPs) were prepared by HAuCl(4), 2-mercaptonicotinic acid (MNA) and erythromycin. Erythromycin and MNA were used as template molecule and functional monomer, respectively. They were first assembled on the surface of GR-AuNPs/CS-PtNPs/gold electrode by the formation of Au-S bonds and hydrogen-bonding interactions. Then the MIPs were formed by electropolymerization of HAuCl(4), MNA and erythromycin. The sensor was characterized by cyclic voltammetry (CV), scanning electron microscope (SEM), UV-visible (UV-vis) absorption speactra and amperometry. The linear range of the sensor was from 7.0 × 10(-8)mol/L-9.0 × 10(-5)mol/L, with the limit of detection (LOD) of 2.3 × 10(-8)mol/L (S/N=3). The sensor showed high selectivity, excellent stability and good reproducibility for the determination of erythromycin, and it was successfully applied to the detection of erythromycin in real spiked samples. Copyright © 2012 Elsevier B.V. All rights reserved.

A novel HPLC fluorescence method for the quantification of methylphenidate in human plasma

PubMed Central

Zhu, Hao-Jie; Wang, Jun-Sheng; Patrick, Kennerly S.; Donovan, Jennifer L.; DeVane, C. Lindsay; Markowitz, John S.

2007-01-01

A number of analytical methods have been established to quantify methylphenidate (MPH). However, to date no HPLC methods are applicable to human pharmacokinetic studies without the use of mass spectrometry (MS) detection. We developed a sensitive and reliable HPLC-fluorescence method for the determination of MPH in human plasma using 4-(4,5-diphenyl-1H-imidazol-2-yl) benzoyl chloride (DIB-Cl) as the derivatizing agent. An established GC-MS method was adopted in this study as a comparator assay. MPH was derivatized DIB-Cl, and separated isocratically on a C18 column using a HPLC system with fluorescence detection (λex: 330 nm, λem: 460 nm). The lower limit of determination was found to be 1 ng/mL. A linear calibration curve was obtained over the concentrations ranging from 1 to 80 ng/mL (r=0.998). The relative standard deviations of intra-day and inter-day variations were ≤ 9.10 % and ≤ 7.58 %, respectively. The accuracy ranged between 92.59 % and 103.06 %. The method was successfully applied to the pharmacokinetic study of a subject who received a single oral dose (0.3 mg/kg) of immediate-release MPH and yielded consistent results with that of the GC-MS method. This method is the first HPLC assay with non-MS detection providing sufficient reliability and sensitivity for both pre-clinical and clinical studies of MPH. PMID:17804308

Salty taste deficits in CALHM1 knockout mice.

PubMed

Tordoff, Michael G; Ellis, Hillary T; Aleman, Tiffany R; Downing, Arnelle; Marambaud, Philippe; Foskett, J Kevin; Dana, Rachel M; McCaughey, Stuart A

2014-07-01

Genetic ablation of calcium homeostasis modulator 1 (CALHM1), which releases adenosine triphosphate from Type 2 taste cells, severely compromises the behavioral and electrophysiological responses to tastes detected by G protein-coupled receptors, such as sweet and bitter. However, the contribution of CALHM1 to salty taste perception is less clear. Here, we evaluated several salty taste-related phenotypes of CALHM1 knockout (KO) mice and their wild-type (WT) controls: 1) In a conditioned aversion test, CALHM1 WT and KO mice had similar NaCl avoidance thresholds. 2) In two-bottle choice tests, CALHM1 WT mice showed the classic inverted U-shaped NaCl concentration-preference function but CALHM1 KO mice had a blunted peak response. 3) In brief-access tests, CALHM1 KO mice showed less avoidance than did WT mice of high concentrations of NaCl, KCl, NH(4)Cl, and sodium lactate (NaLac). Amiloride further ameliorated the NaCl avoidance of CALHM1 KO mice, so that lick rates to a mixture of 1000 mM NaCl + 10 µM amiloride were statistically indistinguishable from those to water. 4) Relative to WT mice, CALHM1 KO mice had reduced chorda tympani nerve activity elicited by oral application of NaCl, NaLac, and sucrose but normal responses to HCl and NH(4)Cl. Chorda tympani responses to NaCl and NaLac were amiloride sensitive in WT but not KO mice. These results reinforce others demonstrating that multiple transduction pathways make complex, concentration-dependent contributions to salty taste perception. One of these pathways depends on CALHM1 to detect hypertonic NaCl in the mouth and signal the aversive taste of concentrated salt. © The Author 2014. Published by Oxford University Press. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Salty Taste Deficits in CALHM1 Knockout Mice

PubMed Central

Ellis, Hillary T.; Aleman, Tiffany R.; Downing, Arnelle; Marambaud, Philippe; Foskett, J. Kevin; Dana, Rachel M.; McCaughey, Stuart A.

2014-01-01

Genetic ablation of calcium homeostasis modulator 1 (CALHM1), which releases adenosine triphosphate from Type 2 taste cells, severely compromises the behavioral and electrophysiological responses to tastes detected by G protein–coupled receptors, such as sweet and bitter. However, the contribution of CALHM1 to salty taste perception is less clear. Here, we evaluated several salty taste–related phenotypes of CALHM1 knockout (KO) mice and their wild-type (WT) controls: 1) In a conditioned aversion test, CALHM1 WT and KO mice had similar NaCl avoidance thresholds. 2) In two-bottle choice tests, CALHM1 WT mice showed the classic inverted U-shaped NaCl concentration-preference function but CALHM1 KO mice had a blunted peak response. 3) In brief-access tests, CALHM1 KO mice showed less avoidance than did WT mice of high concentrations of NaCl, KCl, NH4Cl, and sodium lactate (NaLac). Amiloride further ameliorated the NaCl avoidance of CALHM1 KO mice, so that lick rates to a mixture of 1000mM NaCl + 10 µM amiloride were statistically indistinguishable from those to water. 4) Relative to WT mice, CALHM1 KO mice had reduced chorda tympani nerve activity elicited by oral application of NaCl, NaLac, and sucrose but normal responses to HCl and NH4Cl. Chorda tympani responses to NaCl and NaLac were amiloride sensitive in WT but not KO mice. These results reinforce others demonstrating that multiple transduction pathways make complex, concentration-dependent contributions to salty taste perception. One of these pathways depends on CALHM1 to detect hypertonic NaCl in the mouth and signal the aversive taste of concentrated salt. PMID:24846212

Effect of additives on the volatility of elements in a DC arc during the atomic emission analysis of nickel(II) oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zolotareva, N.I.; Kuzyakov, Yu.Ya.; Khlystova, A.D.

1986-10-20

The authors have studied the effect of traditional halogenating additives, AgCl, CdF/sub 2/, PTFE and that of an effective additive they have selected, ZnF/sub 2/, on the volatility of impurity elements, viz. tungsten, molybdenum, titanium, and zirconium from nickel (II) oxide, and determined the constants for the average relative volatility of the elements by the method of Kantor and Pungor. The results have been used to lower the limits of detection of the impurities cited in nickel(II) oxide.

Acute Toxicity of Smoke Screen Materials to Aquatic Organisms, White Phosphorus-Felt, Red Phosphorus-Butyl Rubber and SGF (Smoke Generator Fuel) No. 2 Fog Oil

DTIC Science & Technology

1986-04-01

anions (F’, Cl’, Br , N83%, S042-) in the water matrices. Detection limits were 0.02 mg/L for phosphate -P and 0.01 mg/L for phosphite -P...resulted in a lower ratio of phosphate to total P and also a lower ratio of phosphite to phosphate . Static and bubbling procedures and the resulting...testing, respectively. Changes with dilution in percentage of P as phosphate or phosphite were minor when ana- lyzed fresh and precipitation had not

Aqueous geochemical data from the analysis of stream-water samples collected in June and August 2008—Taylor Mountains 1:250,000- and Dillingham D-4 1:63,360-scale quadrangles, Alaska

USGS Publications Warehouse

Wang, Bronwen; Owens, Victoria; Bailey, Elizabeth; Lee, Greg

2011-01-01

We report on the chemical analysis of water samples collected from the Taylor Mountains 1:250,000- and Dillingham D-4 1:63,360-scale quadrangles, Alaska. Reported parameters include pH, conductivity, water temperature, major cation and anion concentrations, and trace-element concentrations. We collected the samples as part of a multiyear U.S. Geological Survey project entitled "Geologic and Mineral Deposit Data for Alaskan Economic Development." Data presented here are from samples collected in June and August 2008. Minimal interpretation accompanies this data release. This is the fourth release of aqueous geochemical data from this project; data from samples collected in 2004, 2005, and 2006 were published previously. The data in this report augment but do not duplicate or supersede the previous data releases. Site selection was based on a regional sampling strategy that focused on first- and second-order drainages. Water sample sites were selected on the basis of landscape parameters that included physiography, wetland extent, lithological changes, and a cursory field review of mineralogy from pan concentrates. Stream water in the study area is dominated by bicarbonate (HCO3-), although in a few samples more than 50 percent of the anionic charge can be attributed to sulfate (SO42-). The major-cation chemistry of these samples ranges from Ca2+-Mg2+ dominated to a mix of Ca2+-Mg2+-Na++K2+. In most cases, analysis of duplicate samples showed good agreement for the major cation and major anions with the exception of the duplicate samples at site 08TA565. At site 08TA565, Ca, Mg, Cl, and CaCO3 exceeded 25 percent and the concentrations of trace elements As, Fe and Mn also exceeded 25 percent in this duplicate pair. Chloride concentration varied by more than 25 percent in 5 of the 11 duplicated samples. Trace-element concentrations in these samples generally were at or near the detection limit for the method used and, except for Co at site 08TA565, generally good agreement was determined between duplicate samples for elements with detectable concentrations. Major-ion concentrations were below detection limits in all field blanks, and the trace-element concentrations also were generally below detection limits; however, Co, Mn, Na, Zn, Cl, and Hg were detected in one or more field blank samples.

Co-metal-organic-frameworks with pure uniform crystal morphology prepared via Co2+ exchange-mediated transformation from Zn-metallogels for luminol catalysed chemiluminescence.

PubMed

Tang, Xue Qian; Xiao, Bo Wen; Li, Chun Mei; Wang, Dong Mei; Huang, Cheng Zhi; Li, Yuan Fang

2017-03-15

Cation exchange-mediated transformation from Zn-metallogels (MOGs), which was a mild facile strategy relative to the demanding hydrothermal method, was employed to develop Co 2+ metal-organic frameworks (Co-MOFs) at room temperature. The obtained Co-MOFs was of uniform octahedral morphology and possessed high activity to catalyze luminol chemiluminescence without extra oxidants. By adding cysteine, the CL emission of luminol-Co-MOFs system was further enhanced. Based on this phenomenon, Co-MOFs was utilized to build a practical sensing platform for cysteine determination. Under the optimized conditions, the relative CL intensity (ΔI) was proportional to the concentration of cysteine in the range of 2-10μM, and the detection limit was 0.49μM (3S/N). Moreover, the established method was applied to the determination of cysteine in commercially available pharmaceutical injections. Copyright © 2016 Elsevier B.V. All rights reserved.

Preconcentration of aqueous dyes through phase-transfer liquid-phase microextraction with a room-temperature ionic liquid.

PubMed

Chen, Hsiu-Liang; Chang, Shuo-Kai; Lee, Chia-Ying; Chuang, Li-Lin; Wei, Guor-Tzo

2012-09-12

In this study, we employed the room-temperature ionic liquid [bmim][PF(6)] as both ion-pair agent and an extractant in the phase-transfer liquid-phase microextraction (PTLPME) of aqueous dyes. In the PTLPME method, a dye solution was added to the extraction solution, comprising a small amount of [bmim][PF(6)] in a relatively large amount of CH(2)Cl(2), which serves as the disperser solvent to an extraction solution. Following extraction, CH(2)Cl(2) was evaporated from the extractant, resulting in the extracted dyes being concentrated in a small volume of the ionic liquid phase to increase the enrichment factor. The enrichment factors of for the dye Methylene Blue, Neutral Red, and Methyl Red were approximately 500, 550 and 400, respectively; their detection limits were 0.014, 0.43, and 0.02 μg L(-1), respectively, with relative standard deviations of 4.72%, 4.20%, and 6.10%, respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, J.; Hurtubise, R.J.

A new kind of solid matrix, glasses from sugars, was developed for trace organic analysis. Clear glasses of glucose and trehalose were prepared by evaporating the sugar solutions onto solid supports. It was determined that the ratio of methanol to water was very important in forming a clear glass. Also, glasses made from pure trehalose often cracked. However, with the addition of 8{endash}10{percent} NaCl to the trehalose, no cracks were formed. Clear and rigid glasses of both glucose and trehalose/NaCl were obtained on quartz plates. Strong room-temperature fluorescence (RTF) and room-temperature phosphorescence (RTP) were obtained from benzo[{ital f}]quinoline ({ital B}[{italmore » f}]{ital Q}), 4-phenylphenol (4-PP), B[{ital a}]P-{ital r}-7,{ital t}-8,9,{ital c}-10-tetrahydrotetrol (tetrol I-1), triphenylene, and phenanthrene. The limits of detection (LODs) of both the RTF and RTP for 4-PP and B[{ital f}]Q in the glasses were in the subnanogram/milligram range. {copyright} {ital 1996 Society for Applied Spectroscopy.}« less

Matrix-elimination with steam distillation for determination of short-chain fatty acids in hypersaline waters from pre-salt layer by ion-exclusion chromatography.

PubMed

Ferreira, Fernanda N; Carneiro, Manuel C; Vaitsman, Delmo S; Pontes, Fernanda V M; Monteiro, Maria Inês C; Silva, Lílian Irene D da; Neto, Arnaldo Alcover

2012-02-03

A method for determination of formic, acetic, propionic and butyric acids in hypersaline waters by ion-exclusion chromatography (IEC), using steam distillation to eliminate matrix-interference, was developed. The steam distillation variables such as type of solution to collect the distillate, distillation time and volume of the 50% v/v H₂SO₄ solution were optimized. The effect of the addition of NaCl different concentrations to the calibration standards on the carboxylic acid recovery was also investigated. Detection limits of 0.2, 0.5, 0.3 and 1.5 mg L⁻¹ were obtained for formic, acetic, propionic and butyric acids, respectively. Produced waters from petroleum reservoirs in the Brazilian pre-salt layer containing about 19% m/v of NaCl were analyzed. Good recoveries (99-108%) were obtained for all acids in spiked produced water samples. Copyright © 2011 Elsevier B.V. All rights reserved.

A novel flow injection chemiluminescence method for automated and miniaturized determination of phenols in smoked food samples.

PubMed

Vakh, Christina; Evdokimova, Ekaterina; Pochivalov, Aleksei; Moskvin, Leonid; Bulatov, Andrey

2017-12-15

An easily performed fully automated and miniaturized flow injection chemiluminescence (CL) method for determination of phenols in smoked food samples has been proposed. This method includes the ultrasound assisted solid-liquid extraction coupled with gas-diffusion separation of phenols from smoked food sample and analytes absorption into a NaOH solution in a specially designed gas-diffusion cell. The flow system was designed to focus on automation and miniaturization with minimal sample and reagent consumption by inexpensive instrumentation. The luminol - N-bromosuccinimide system in an alkaline medium was used for the CL determination of phenols. The limit of detection of the proposed procedure was 3·10 -8 ·molL -1 (0.01mgkg -1 ) in terms of phenol. The presented method demonstrated to be a good tool for easy, rapid and cost-effective point-of-need screening phenols in smoked food samples. Copyright © 2017 Elsevier Ltd. All rights reserved.

Potassium permanganate-glutaraldehyde chemiluminescence system catalyzed by gold nanoprisms toward selective determination of fluoride.

PubMed

Abolhasani, Jafar; Hassanzadeh, Javad; Ghorbani-Kalhor, Ebrahim

2016-02-01

Gold and silver nanoparticles (NPs) are shown to exert a positive effect on the chemiluminescence (CL) reaction of permanganate aldehydes. Interestingly, between various shapes examined, Au nanoprisms have the highest beneficial effect. This effect is even more notable in the presence of sodium dodecyl sulfate (SDS) surfactant. UV-vis spectra and transmission electron microscopy were used to characterize the NP shapes and sizes. Furthermore, it was observed that iron(III) ions can slightly increase CL emission of this system. This intensification is very effective in the presence of fluoride ions (F(-)). These observations form the basis of the method for the high sensitive determination of F(-) in the 6-1200 nmol L(-1) concentration range, with a detection limit of 2.1 nmol L(-1). The proposed method has good precision and was satisfactorily used in the selective determination of low concentrations of fluoride ion in real samples. Copyright © 2015 John Wiley & Sons, Ltd.

Synchronized flash photolysis and pulse deposition in matrix isolation experiments

NASA Technical Reports Server (NTRS)

Allamandola, Louis J.; Lucas, Donald; Pimentel, George C.

1978-01-01

An apparatus is described which permits flash photolysis of a pulse-deposited gas mixture in a matrix isolation experiment. This technique obviates the limitations of in situ photolysis imposed by the cage effect and by secondary photolysis. The matrix is deposited in pulses at 30-s intervals and photolyzed sequentially by four synchronized flashlamps approximately 1 ms before the pulse strikes the cold surface. Pulsed deposition maintains adequate isolation and causes line narrowing, which enhances spectral sensitivity. The efficacy of flash photolysis combined with pulsed deposition for producing and trapping transient species was demonstrated by infrated detection of CF3 (from photolysis of CF3I/Ar mixtures) and of ClCO (from photolysis of Cl2/CO/Ar mixtures). The apparatus was used to study the photolytic decomposition of gaseous tricarbonylironcyclobutadiene, C4H4Fe(CO)3. The results indicate that the primary photolytic step is not elimination of C4H4, as suggested earlier, but rather of CO.

Environmental and health risks of chlorine trifluoride (ClF3), an alternative to potent greenhouse gases in the semiconductor industry.

PubMed

Tsai, Wen-Tien

2011-06-15

The first accident involving chlorine trifluoride (ClF(3)) in the history of semiconductor fabrication processes occurred on 28 July 2006 at Hsinchu (Taiwan), resulting in a large release of the highly reactive material and causing the chemical burn to several workers. ClF(3) is used primarily as an in situ cleaning gas in the manufacture of semiconductor silicon-wafer devices in replacement of perfluorocompounds (PFCs) because they have the high potential to contribute significantly to the global warming. This article aimed at reviewing ClF(3) in the physicochemical properties, the industrial uses, and the environmental implications on the basis of its toxicity, reactivity, health hazards and exposure limits. The health hazards of probable decomposition/hydrolysis products from ClF(3) were also evaluated based on their basic physicochemical properties and occupational exposure limits. The occupational exposure assessment was further discussed to understand potentially hazardous risks caused by hydrogen fluoride and fluorides from the decomposition/hydrolysis products of ClF(3). Copyright © 2010 Elsevier B.V. All rights reserved.

Measurements of the liquidus surface and solidus transitions of the NaCl-UCl3 and NaCl-UCl3-CeCl3 phase diagrams

NASA Astrophysics Data System (ADS)

Sooby, E. S.; Nelson, A. T.; White, J. T.; McIntyre, P. M.

2015-11-01

NaCl-UCl3-PuCl3 is proposed as the fuel salt for a number of molten salt reactor concepts. No experimental data exists for the ternary system, and limited data is available for the binary compositions of this salt system. Differential scanning calorimetry is used in this study to examine the liquidus surface and solidus transition of a surrogate fuel-salt (NaCl-UCl3-CeCl3) and to reinvestigate the NaCl-UCl3 eutectic phase diagram. The results of this study show good agreement with previously reported data for the pure salt compounds used (NaCl, UCl3, and CeCl3) as well as for the eutectic points for the NaCl-UCl3 and NaCl-CeCl3 binary systems. The NaCl-UCl3 liquidus surface produced in this study predicts a 30-40 °C increase on the NaCl-rich side of the binary phase diagram. The increase in liquidus temperature could prove significant to molten salt reactor modeling.

Oxalyl chloride, ClC(O)C(O)Cl: UV/vis spectrum and Cl atom photolysis quantum yields at 193, 248, and 351 nm

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghosh, Buddhadeb; Papanastasiou, Dimitrios K.; Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, Colorado 80309

2012-10-28

Oxalyl chloride, (ClCO){sub 2}, has been used as a Cl atom photolytic precursor in numerous laboratory kinetic and photochemical studies. In this study, the UV/vis absorption spectrum of (ClCO){sub 2} and the Cl atom quantum yields in its photolysis at 193, 248, and 351 nm are reported. The UV/vis spectrum was measured between 200 and 450 nm at 296 K using diode array spectroscopy in conjunction with an absolute cross section obtained at 213.9 nm. Our results are in agreement with the spectrum reported by Baklanov and Krasnoperov [J. Phys. Chem. A 105, 97-103 (2001)], which was obtained at 11more » discrete wavelengths between 193.3 and 390 nm. Cl atom quantum yields, {Phi}({lambda}), were measured using pulsed laser photolysis coupled with time resolved atomic resonance fluorescence detection of Cl. The UV photolysis of (ClCO){sub 2} has been shown in previous studies to occur via an impulsive three-body dissociation mechanism, (COCl){sub 2}+ hv{yields} ClCO*+ Cl + CO (2), where the excited ClCO radical, ClCO*, either dissociates or stabilizes ClCO*{yields} Cl + CO (3a), {yields} ClCO (3b). ClCO is thermally unstable at the temperatures (253-298 K) and total pressures (13-128 Torr) used in our experiments ClCO + M {yields} Cl + CO + M (4) leading to the formation of a secondary Cl atom that was resolvable in the Cl atom temporal profiles obtained in the 248 and 351 nm photolysis of (ClCO){sub 2}. {Phi}(193 nm) was found to be 2.07 {+-} 0.37 independent of bath gas pressure (25.8-105.7 Torr, N{sub 2}), i.e., the branching ratio for channel 2a or the direct formation of 2Cl + 2CO in the photolysis of (ClCO){sub 2} is >0.95. At 248 nm, the branching ratio for channel 2a was determined to be 0.79 {+-} 0.15, while the total Cl atom yield, i.e., following the completion of reaction (4), was found to be 1.98 {+-} 0.26 independent of bath gas pressure (15-70 Torr, N{sub 2}). {Phi}(351 nm) was found to be pressure dependent between 7.8 and 122.4 Torr (He, N{sub 2}). The low-pressure limit of the total Cl atom quantum yield, {Phi}{sub 0}(351 nm), was 2.05 {+-} 0.24. As part of this work, rate coefficients for the thermal decomposition of ClCO were measured between 253 and 298 K at total pressures between 13 and 128 Torr (He and N{sub 2} bath gases). The N{sub 2} bath gas results were combined with the data reported in Nicovich et al. [J. Chem. Phys. 92, 3539-3544 (1990)] to yield k{sub 4}(T, N{sub 2}) = (4.7 {+-} 0.7) Multiplication-Sign 10{sup -10} exp [-(2987 {+-} 16)/T] cm{sup 3} molecule{sup -1} s{sup -1}, while the He bath gas data fit yielded k{sub 4}(T, He) = (2.3 {+-} 2.1) Multiplication-Sign 10{sup -10} exp [-(2886 {+-} 218)/T] cm{sup 3} molecule{sup -1} s{sup -1}. The quoted uncertainties are at the 2{sigma} level from the precision of the fit. In addition, the room temperature rate coefficient for the Cl + ClNO reaction was measured in this work to be (1.03 {+-} 0.10) Multiplication-Sign 10{sup -10} cm{sup 3} molecule{sup -1} s{sup -1}.« less

In situ self-assembly of gold nanoparticles on hydrophilic and hydrophobic substrates for influenza virus-sensing platform

NASA Astrophysics Data System (ADS)

Ahmed, Syed Rahin; Kim, Jeonghyo; Tran, Van Tan; Suzuki, Tetsuro; Neethirajan, Suresh; Lee, Jaebeom; Park, Enoch Y.

2017-03-01

Nanomaterials without chemical linkers or physical interactions that reside on a two-dimensional surface are attractive because of their electronic, optical and catalytic properties. An in situ method has been developed to fabricate gold nanoparticle (Au NP) films on different substrates, regardless of whether they are hydrophilic or hydrophobic surfaces, including glass, 96-well polystyrene plates, and polydimethylsiloxane (PDMS). A mixture of sodium formate (HCOONa) and chloroauric acid (HAuCl4) solution was used to prepare Au NP films at room temperature. An experimental study of the mechanism revealed that film formation is dependent on surface wettability and inter particle attraction. The as-fabricated Au NP films were further applied to the colorimetric detection of influenza virus. The response to the commercial target, New Caledonia/H1N1/1999 influenza virus, was linear in the range from 10 pg/ml to 10 μg/ml and limit of detection was 50.5 pg/ml. In the presence of clinically isolated influenza A virus (H3N2), the optical density of developed color was dependent on the virus concentration (10-50,000 PFU/ml). The limit of detection of this study was 24.3 PFU/ml, a limit 116 times lower than that of conventional ELISA (2824.3 PFU/ml). The sensitivity was also 500 times greater than that of commercial immunochromatography kits.

The Generation and Detection of Rydberg Wavepackets

NASA Astrophysics Data System (ADS)

Meyler, P. E.

Available from UMI in association with The British Library. Requires signed TDF. A Rydberg wavepacket is a coherent superposition of several electronic energy eigenstates corresponding to the high lying energy levels of an atom. In this thesis, an experiment is described in which a radially localized Rydberg wavepacket is excited in atomic rubidium by a picosecond optical pump pulse. The wavepacket has a mean effective principal quantum number v_0 = 62, which corresponds to a classical orbit period T _{rm cl} = 37 ps. The subsequent evolution of the wavepacket is probed by a delayed, picosecond optical pulse. The resulting photoionization signal is measured as a function of pump-probe delay, and initially displays peaks separated by T_{rm cl}. This classical oscillation then collapses, after which a fractional revival of period T_ {rm cl}/2 is observed, followed finally by a full revival of the wavepacket. These results constitute the first experimental observation of a fractional revival in any system, and are shown to be in good agreement with theoretical predictions. The results of the experiment are discussed with reference to the correspondence principle and it is concluded that even in the limit of large quantum numbers, the evolution of a given system can be dominated by quantum mechanical effects.

Cosmological Parameters from the QUAD CMB Polarization Experiment

NASA Astrophysics Data System (ADS)

Castro, P. G.; Ade, P.; Bock, J.; Bowden, M.; Brown, M. L.; Cahill, G.; Church, S.; Culverhouse, T.; Friedman, R. B.; Ganga, K.; Gear, W. K.; Gupta, S.; Hinderks, J.; Kovac, J.; Lange, A. E.; Leitch, E.; Melhuish, S. J.; Memari, Y.; Murphy, J. A.; Orlando, A.; Pryke, C.; Schwarz, R.; O'Sullivan, C.; Piccirillo, L.; Rajguru, N.; Rusholme, B.; Taylor, A. N.; Thompson, K. L.; Turner, A. H.; Wu, E. Y. S.; Zemcov, M.; QUa D Collaboration

2009-08-01

In this paper, we present a parameter estimation analysis of the polarization and temperature power spectra from the second and third season of observations with the QUaD experiment. QUaD has for the first time detected multiple acoustic peaks in the E-mode polarization spectrum with high significance. Although QUaD-only parameter constraints are not competitive with previous results for the standard six-parameter ΛCDM cosmology, they do allow meaningful polarization-only parameter analyses for the first time. In a standard six-parameter ΛCDM analysis, we find the QUaD TT power spectrum to be in good agreement with previous results. However, the QUaD polarization data show some tension with ΛCDM. The origin of this 1σ-2σ tension remains unclear, and may point to new physics, residual systematics, or simple random chance. We also combine QUaD with the five-year WMAP data set and the SDSS luminous red galaxies 4th data release power spectrum, and extend our analysis to constrain individual isocurvature mode fractions, constraining cold dark matter density, αcdmi < 0.11 (95% confidence limit (CL)), neutrino density, αndi < 0.26 (95% CL), and neutrino velocity, αnvi < 0.23 (95% CL), modes. Our analysis sets a benchmark for future polarization experiments.

Effects of cerebrolysin on motor-neuron-like NSC-34 cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keilhoff, Gerburg, E-mail: Gerburg.keilhoff@med.ovgu.de; Lucas, Benjamin; Pinkernelle, Josephine

Although the peripheral nervous system is capable of regeneration, this capability is limited. As a potential means of augmenting nerve regeneration, the effects of cerebrolysin (CL) – a proteolytic peptide fraction – were tested in vitro on the motor-neuron-like NSC-34 cell line and organotypic spinal cord cultures. Therefore, NSC-34 cells were subjected to mechanical stress by changing media and metabolic stress by oxygen glucose deprivation. Afterwards, cell survival/proliferation using MTT and BrdU-labeling (FACS) and neurite sprouting using ImageJ analysis were evaluated. Calpain-1, Src and α-spectrin protein expression were analyzed by Western blot. In organotypic cultures, the effect of CL onmore » motor neuron survival and neurite sprouting was tested by immunohistochemistry. CL had a temporary anti-proliferative but initially neuroprotective effect on OGD-stressed NSC-34 cells. High-dosed or repeatedly applied CL was deleterious for cell survival. CL amplified neurite reconstruction to limited extent, affected calpain-1 protein expression and influenced calpain-mediated spectrin cleavage as a function of Src expression. In organotypic spinal cord slice cultures, CL was not able to support motor neuron survival/neurite sprouting. Moreover, it hampered astroglia and microglia activities. The data suggest that CL may have only isolated positive effects on injured spinal motor neurons. High-dosed or accumulated CL seemed to have adverse effects in treatment of spinal cord injury. Further experiments are required to optimize the conditions for a safe clinical administration of CL in spinal cord injuries. - Highlights: • Cerebrolysin (CL) is anti-proliferative but initially neuroprotective in OGD-stressed NSC-34 cells. • CL amplified neurite reconstruction of NSC-34 cells. • CL affected calpain-1 expression and calpain-mediated spectrin cleavage as function of Src expression. • In organotypic spinal cord cultures, CL hampered motor neuron survival and glia activity. • Findings pose a contraindication for unchallenged use of CL in spinal cord injuries.« less

Light and variable 37Cl/35Cl ratios in rocks from Gale Crater, Mars: Possible signature of perchlorate

NASA Astrophysics Data System (ADS)

Farley, K. A.; Martin, P.; Archer, P. D.; Atreya, S. K.; Conrad, P. G.; Eigenbrode, J. L.; Fairén, A. G.; Franz, H. B.; Freissinet, C.; Glavin, D. P.; Mahaffy, P. R.; Malespin, C.; Ming, D. W.; Navarro-Gonzalez, R.; Sutter, B.

2016-03-01

Cl isotope ratios measured on HCl thermally evolved from as-yet-unknown phases in sedimentary rocks and sand in Gale Crater provide unexpected insights to the Martian surficial Cl cycle. The seven samples yield δ37Cl values ranging from - 1 ± 25 ‰ to - 51 ± 5 ‰. Five analyses from two samples of the Sheepbed mudstone (Yellowknife Bay study area) are analytically indistinguishable with a mean δ37Cl of - 11 ± 7 ‰ (1 σ). In contrast, four mudstones/sandstones from the Kimberley and Pahrump study areas also yielded indistinguishable ratios, but with a mean δ37Cl of - 43 ± 6 ‰. The Rocknest sand deposit gave a highly uncertain δ37Cl value of - 7 ± 44 ‰. These light and highly variable δ37Cl values are unique among known solar system materials. Two endmember models are offered to account for these observations, and in both, perchlorate, with its extreme ability to fractionate Cl isotopes, is critical. In the first model, SAM is detecting HCl from an oxychlorine compound (e.g., perchlorate) produced from volcanic gas emissions by atmospheric chemical reactions. Similar reactions in Earth's atmosphere may be responsible for the isotopically lightest known Cl outside of this study, in perchlorate from the Atacama Desert. Some of the Gale Crater δ37Cl values are more negative than those in Atacama perchlorate, but because reaction mechanisms and associated fractionation factors are unknown, it is impossible to assess whether this difference is prohibitive. If the negative δ37Cl signal is produced in this fashion, the isotopic variability among samples could arise either from variations in the relative size of the reactant chloride and product perchlorate reservoirs, or from variations in the fraction of perchlorate reduced back to chloride after deposition. Such reduction strongly enriches 37Cl in the residual perchlorate. Perchlorate reduction alone offers an alternative endmember model that can explain the observed data if SAM measured HCl derived from chloride. In this model isotopically normal perchlorate produced by an unspecified mechanism is reduced to chloride. Depending on the relative size of the reduced reservoir, the integrated product chloride can vary in isotopic composition from - 70 ‰ in the first increment all the way to the starting composition if the perchlorate is fully reduced. Thus, variable degrees of perchlorate reduction can produce chloride with the appropriate δ37Cl range. Combination of the two endmember models, in which the perchlorate subject to post-deposition reduction is isotopically negative from atmospheric reactions, is also possible. Determination of the phase hosting the Cl measured by SAM, an oxychlorine compound or chloride, is critical for selecting between these models, and for developing implications of the results for the Mars surficial Cl cycle. At present it is not possible to conclusively establish which phase is responsible (possibly both), but limited evidence favors the conclusion that the measured Cl derives mostly from an oxychlorine compound.

Inhalation a significant exposure route for chlorinated organophosphate flame retardants.

PubMed

Schreder, Erika D; Uding, Nancy; La Guardia, Mark J

2016-05-01

Chlorinated organophosphate flame retardants (ClOPFRs) are widely used as additive flame retardants in consumer products including furniture, children's products, building materials, and textiles. Tests of indoor media in homes, offices, and other environments have shown these compounds are released from products and have become ubiquitous indoor pollutants. In house dust samples from Washington State, U.S.A., ClOPFRs were the flame retardants detected in the highest concentrations. Two ClOPFRs, tris(1,3-dichloro-2-propyl)phosphate (TDCPP or TDCIPP) and tris(2-chloroethyl)phosphate (TCEP), have been designated as carcinogens, and there is growing concern about the toxicity of the homologue tris(1-chloro-2-propyl)phosphate (TCPP or TCIPP). In response to concerns about exposure to these compounds, the European Union and a number of U.S. states have taken regulatory action to restrict their use in certain product categories. To better characterize exposure to ClOPFRs, inhalation exposure was assessed using active personal air samplers in Washington State with both respirable and inhalable particulate fractions collected to assess the likelihood particles penetrate deep into the lungs. Concentrations of ∑ClOPFRs (respirable and inhalable) ranged from 97.1 to 1190 ng m(-3) (mean 426 ng m(-3)), with TCPP detected at the highest concentrations. In general, higher levels were detected in the inhalable particulate fraction. Total intake of ClOPFRs via the inhalation exposure route was estimated to exceed intake via dust ingestion, indicating that inhalation is an important route that should be taken into consideration in assessments of these compounds. Copyright © 2015 Elsevier Ltd. All rights reserved.

LabVIEW-based control and data acquisition system for cathodoluminescence experiments.

PubMed

Bok, J; Schauer, P

2011-11-01

Computer automation of cathodoluminescence (CL) experiments using equipment developed in our laboratory is described. The equipment provides various experiments for CL efficiency, CL spectra, and CL time response studies. The automation was realized utilizing the graphical programming environment LabVIEW. The developed application software with procedures for equipment control and data acquisition during various CL experiments is presented. As the measured CL data are distorted by technical limitations of the equipment, such as equipment spectral sensitivity and time response, data correction algorithms were incorporated into the procedures. Some examples of measured data corrections are presented. © 2011 American Institute of Physics

Waste-water impacts on groundwater: Cl/Br ratios and implications for arsenic pollution of groundwater in the Bengal Basin and Red River Basin, Vietnam.

PubMed

McArthur, J M; Sikdar, P K; Hoque, M A; Ghosal, U

2012-10-15

Across West Bengal and Bangladesh, concentrations of Cl in much groundwater exceed the natural, upper limit of 10 mg/L. The Cl/Br mass ratios in groundwaters range up to 2500 and scatter along mixing lines between waste-water and dilute groundwater, with many falling near the mean end-member value for waste-water of 1561 at 126 mg/L Cl. Values of Cl/Br exceed the seawater ratio of 288 in uncommon NO(3)-bearing groundwaters, and in those containing measurable amounts of salt-corrected SO(4) (SO(4) corrected for marine salt). The data show that shallow groundwater tapped by tube-wells in the Bengal Basin has been widely contaminated by waste-water derived from pit latrines, septic tanks, and other methods of sanitary disposal, although reducing conditions in the aquifers have removed most evidence of NO(3) additions from these sources, and much evidence of their additions of SO(4). In groundwaters from wells in palaeo-channel settings, end-member modelling shows that >25% of wells yield water that comprises ≥10% of waste-water. In palaeo-interfluvial settings, only wells at the margins of the palaeo-interfluvial sequence contain detectable waste water. Settings are identifiable by well-colour survey, owner information, water composition, and drilling. Values of Cl/Br and faecal coliform counts are both inversely related to concentrations of pollutant As in groundwater, suggesting that waste-water contributions to groundwater in the near-field of septic-tanks and pit-latrines (within 30 m) suppress the mechanism of As-pollution and lessen the prevalence and severity of As pollution. In the far-field of such sources, organic matter in waste-water may increase groundwater pollution by As. Copyright © 2012. Published by Elsevier B.V.

Determination of low levels of perchlorate in lettuce and spinach using ion chromatography-electrospray ionization mass spectrometry (IC-ESI-MS).

PubMed

Seyfferth, Angelia L; Parker, David R

2006-03-22

A sample preparation method was developed to quantify environmentally relevant (low micrograms per liter) concentrations of perchlorate (ClO4(-)) in leafy vegetables using IC-ESI-MS. Lettuce and spinach were macerated, centrifuged, and filtered, and the aqueous extracts were rendered water-clear using a one-step solid-phase extraction method. Total time for extraction and sample preparation was 6 h. Ion suppression was demonstrated and was likely due to unknown organics still present in the extract solution after cleanup. However, this interference was readily eliminated using a Cl(18)O4(-) internal standard at 1 microg/L in all standards and samples. Hydroponically grown perchlorate-free butterhead lettuce was spiked to either 10.3 or 37.7 microg/kg of fresh weight (FW), and recoveries were between 91 and 98% and between 93 and 101%, respectively. Five types of lettuce and spinach from a local grocery store were then analyzed; they contained from 0.6 to 6.4 microg/kg of FW. Spike recoveries using the store-bought samples ranged from 89 to 100%. The method detection limit for perchlorate in plant extracts is 40 ng/L, and the corresponding minimum reporting limit is 200 ng/L or 0.8 microg/kg of FW.

Three-Dimensional Porous Nickel Frameworks Anchored with Cross-Linked Ni(OH)2 Nanosheets as a Highly Sensitive Nonenzymatic Glucose Sensor.

PubMed

Mao, Weiwei; He, Haiping; Sun, Pengcheng; Ye, Zhizhen; Huang, Jingyun

2018-05-02

A facile and scalable in situ microelectrolysis nanofabrication technique is developed for preparing cross-linked Ni(OH) 2 nanosheets on a novel three-dimensional porous nickel template (Ni(OH) 2 @3DPN). For the constructed template, the porogen of NaCl particles not only induces a self-limiting surficial hot corrosion to claim the "start engine stop" mechanism but also serves as the primary battery electrolyte to greatly accelerate the growth of Ni(OH) 2 . As far as we know, the microelectrolysis nanofabrication is superior to the other reported Ni(OH) 2 synthesis methods due to the mild condition (60 °C, 6 h, NaCl solution, ambient environment) and without any post-treatment. The integrated Ni(OH) 2 @3DPN electrode with a highly suitable microstructure and a porous architecture implies a potential application in electrochemistry. As a proof-of-concept demonstration, the electrode was employed for nonenzymatic glucose sensing, which exhibits an outstanding sensitivity of 2761.6 μA mM -1 cm -2 ranging from 0.46 to 2100 μM, a fast response, and a low detection limit. The microelectrolysis nanofabrication is a one-step, binder-free, entirely green, and therefore it has a distinct advantage to improve clean production and reduce energy consumption.

Flow-based analysis using microfluidics-chemiluminescence systems.

PubMed

Al Lawati, Haider A J

2013-01-01

This review will discuss various approaches and techniques in which analysis using microfluidics-chemiluminescence systems (MF-CL) has been reported. A variety of applications is examined, including environmental, pharmaceutical, biological, food and herbal analysis. Reported uses of CL reagents, sample introduction techniques, sample pretreatment methods, CL signal enhancement and detection systems are discussed. A hydrodynamic pumping system is predominately used for these applications. However, several reports are available in which electro-osmotic (EO) pumping has been implemented. Various sample pretreatment methods have been used, including liquid-liquid extraction, solid-phase extraction and molecularly imprinted polymers. A wide range of innovative techniques has been reported for CL signal enhancement. Most of these techniques are based on enhancement of the mixing process in the microfluidics channels, which leads to enhancement of the CL signal. However, other techniques are also reported, such as mirror reaction, liquid core waveguide, on-line pre-derivatization and the use of an opaque white chip with a thin transparent seal. Photodetectors are the most commonly used detectors; however, other detection systems have also been used, including integrated electrochemiluminescence (ECL) and organic photodiodes (OPDs). Copyright © 2012 John Wiley & Sons, Ltd.

Determination of the ortho to para ratio of H2Cl+ and H2O+ from submillimeter observations.

PubMed

Gerin, Maryvonne; de Luca, Massimo; Lis, Dariusz C; Kramer, Carsten; Navarro, Santiago; Neufeld, David; Indriolo, Nick; Godard, Benjamin; Le Petit, Franck; Peng, Ruisheng; Phillips, Thomas G; Roueff, Evelyne

2013-10-03

The opening of the submillimeter sky with the Herschel Space Observatory has led to the detection of new interstellar molecular ions, H2O(+), H2Cl(+), and HCl(+), which are important intermediates in the synthesis of water vapor and hydrogen chloride. In this paper, we report new observations of H2O(+) and H2Cl(+) performed with both Herschel and ground-based telescopes, to determine the abundances of their ortho and para forms separately and derive the ortho-to-para ratio. At the achieved signal-to-noise ratio, the observations are consistent with an ortho-to-para ratios of 3 for both H2O(+) and H2Cl(+), in all velocity components detected along the lines-of-sight to the massive star-forming regions W31C and W49N. We discuss the mechanisms that contribute to establishing the observed ortho-to-para ratio and point to the need for a better understanding of chemical reactions, which are important for establishing the H2O(+) and H2Cl(+) ortho-to-para ratios.

Zepto-molar electrochemical detection of Brucella genome based on gold nanoribbons covered by gold nanoblooms

NASA Astrophysics Data System (ADS)

Rahi, Amid; Sattarahmady, Naghmeh; Heli, Hossein

2015-12-01

Gold nanoribbons covered by gold nanoblooms were sonoelectrodeposited on a polycrystalline gold surface at -1800 mV (vs. AgCl) with the assistance of ultrasound and co-occurrence of the hydrogen evolution reaction. The nanostructure, as a transducer, was utilized to immobilize a Brucella-specific probe and fabrication of a genosensor, and the process of immobilization and hybridization was detected by electrochemical methods, using methylene blue as a redox marker. The proposed method for detection of the complementary sequence, sequences with base-mismatched (one-, two- and three-base mismatches), and the sequence of non-complementary sequence was assayed. The fabricated genosensor was evaluated for the assay of the bacteria in the cultured and human samples without polymerase chain reactions (PCR). The genosensor could detect the complementary sequence with a calibration sensitivity of 0.40 μA dm3 mol-1, a linear concentration range of 10 zmol dm-3 to 10 pmol dm-3, and a detection limit of 1.71 zmol dm-3.

A Reusable Impedimetric Aptasensor for Detection of Thrombin Employing a Graphite-Epoxy Composite Electrode

PubMed Central

Ocaña, Cristina; Pacios, Mercè; del Valle, Manel

2012-01-01

Here, we report the application of a label-free electrochemical aptasensor based on a graphite-epoxy composite electrode for the detection of thrombin; in this work, aptamers were immobilized onto the electrodes surface using wet physical adsorption. The detection principle is based on the changes of the interfacial properties of the electrode; these were probed in the presence of the reversible redox couple [Fe(CN)6]3−/[Fe(CN)6]4− using impedance measurements. The electrode surface was partially blocked due to formation of aptamer-thrombin complex, resulting in an increase of the interfacial electron-transfer resistance detected by Electrochemical Impedance Spectroscopy (EIS). The aptasensor showed a linear response for thrombin in the range of 7.5 pM to 75 pM and a detection limit of 4.5 pM. The aptasensor was regenerated by breaking the complex formed between the aptamer and thrombin using 2.0 M NaCl solution at 42 °C, showing its operation for different cycles. The interference response caused by main proteins in serum has been characterized. PMID:22736991

A novel pyridyl triphenylamine-BODIPY aldoxime: Naked-eye visible and fluorometric chemodosimeter for hypochlorite.

PubMed

Xu, Xiu-Xiu; Qian, Ying

2017-08-05

An aldoxime containing fluorescent probe based on vinylpydine-appended triphenylamine-BODIPY has been designed and used for hypochlorite detection. OX-PPA-BODIPY was developed by introducing an aldoxime group into the 2-position of BODIPY, which can be used for the detection of hypochlorite with a sharp color change from pink to green. The attachment of 4-vinylpyridine moiety to triphenylamine-BODIPY constructs a fluorogen with desirable conjugated system. The probe, which displays extremely weak fluorescence owing to the CN isomerization mechanism at 2-position of BODIPY, responds to HClO/ClO - through a dramatic enhancement of its fluorescence intensity. This new probe, a naked-eye visible and fluorometric chemodosimeter, exhibits high selectivity and sensitivity toward hypochlorite over other reactive oxygen species (ROS) and anions. The detection is accompanied by a 20-fold increase in fluorescent intensity (Φ F from 0.02 to 0.43). The detection limit of the probe for hypochlorite is 7.37×10 -7 M. Moreover, OX-PPA-BODIPY can be used to detect hypochlorite in real water samples. Copyright © 2017 Elsevier B.V. All rights reserved.

A novel pyridyl triphenylamine-BODIPY aldoxime: Naked-eye visible and fluorometric chemodosimeter for hypochlorite

NASA Astrophysics Data System (ADS)

Xu, Xiu-xiu; Qian, Ying

2017-08-01

An aldoxime containing fluorescent probe based on vinylpydine-appended triphenylamine-BODIPY has been designed and used for hypochlorite detection. OX-PPA-BODIPY was developed by introducing an aldoxime group into the 2-position of BODIPY, which can be used for the detection of hypochlorite with a sharp color change from pink to green. The attachment of 4-vinylpyridine moiety to triphenylamine-BODIPY constructs a fluorogen with desirable conjugated system. The probe, which displays extremely weak fluorescence owing to the Cdbnd N isomerization mechanism at 2-position of BODIPY, responds to HClO/ClO- through a dramatic enhancement of its fluorescence intensity. This new probe, a naked-eye visible and fluorometric chemodosimeter, exhibits high selectivity and sensitivity toward hypochlorite over other reactive oxygen species (ROS) and anions. The detection is accompanied by a 20-fold increase in fluorescent intensity (ΦF from 0.02 to 0.43). The detection limit of the probe for hypochlorite is 7.37 × 10- 7 M. Moreover, OX-PPA-BODIPY can be used to detect hypochlorite in real water samples.

Chloromethane release from carbonaceous meteorite affords new insight into Mars lander findings

NASA Astrophysics Data System (ADS)

Keppler, Frank; Harper, David B.; Greule, Markus; Ott, Ulrich; Sattler, Tobias; Schöler, Heinz F.; Hamilton, John T. G.

2014-11-01

Controversy continues as to whether chloromethane (CH3Cl) detected during pyrolysis of Martian soils by the Viking and Curiosity Mars landers is indicative of organic matter indigenous to Mars. Here we demonstrate CH3Cl release (up to 8 μg/g) during low temperature (150-400°C) pyrolysis of the carbonaceous chondrite Murchison with chloride or perchlorate as chlorine source and confirm unequivocally by stable isotope analysis the extraterrestrial origin of the methyl group (δ2H +800 to +1100‰, δ13C -19.2 to +10‰,). In the terrestrial environment CH3Cl released during pyrolysis of organic matter derives from the methoxyl pool. The methoxyl pool in Murchison is consistent both in magnitude (0.044%) and isotope signature (δ2H +1054 +/- 626‰, δ13C +43.2 +/- 38.8‰,) with that of the CH3Cl released on pyrolysis. Thus CH3Cl emissions recorded by Mars lander experiments may be attributed to methoxyl groups in undegraded organic matter in meteoritic debris reaching the Martian surface being converted to CH3Cl with perchlorate or chloride in Martian soil. However we cannot discount emissions arising additionally from organic matter of indigenous origin. The stable isotope signatures of CH3Cl detected on Mars could potentially be utilized to determine its origin by distinguishing between terrestrial contamination, meteoritic infall and indigenous Martian sources.

Chloromethane release from carbonaceous meteorite affords new insight into Mars lander findings.

PubMed

Keppler, Frank; Harper, David B; Greule, Markus; Ott, Ulrich; Sattler, Tobias; Schöler, Heinz F; Hamilton, John T G

2014-11-13

Controversy continues as to whether chloromethane (CH3Cl) detected during pyrolysis of Martian soils by the Viking and Curiosity Mars landers is indicative of organic matter indigenous to Mars. Here we demonstrate CH3Cl release (up to 8 μg/g) during low temperature (150-400°C) pyrolysis of the carbonaceous chondrite Murchison with chloride or perchlorate as chlorine source and confirm unequivocally by stable isotope analysis the extraterrestrial origin of the methyl group (δ(2)H +800 to +1100‰, δ(13)C -19.2 to +10‰,). In the terrestrial environment CH3Cl released during pyrolysis of organic matter derives from the methoxyl pool. The methoxyl pool in Murchison is consistent both in magnitude (0.044%) and isotope signature (δ(2)H +1054 ± 626‰, δ(13)C +43.2 ± 38.8‰,) with that of the CH3Cl released on pyrolysis. Thus CH3Cl emissions recorded by Mars lander experiments may be attributed to methoxyl groups in undegraded organic matter in meteoritic debris reaching the Martian surface being converted to CH3Cl with perchlorate or chloride in Martian soil. However we cannot discount emissions arising additionally from organic matter of indigenous origin. The stable isotope signatures of CH3Cl detected on Mars could potentially be utilized to determine its origin by distinguishing between terrestrial contamination, meteoritic infall and indigenous Martian sources.

Oxychlorine Species in Gale Crater and Broader Implications for Mars

NASA Technical Reports Server (NTRS)

Ming, Douglas W.; Sutter, Brad; Morris, Richard V.; Clark, B. C.; Mahaffy, P. H.; Archilles, C.; Wray, J. J.; Fairen, A. G.; Gellert, Ralf; Yen, Albert;

Oxychlorine species in Gale Crater and broader implications for Mars

NASA Astrophysics Data System (ADS)

Archer, Paul Douglas; Hogancamp, Joanna C.; Ming, Douglas W.; Sutter, Brad; Morris, Richard V.; Clark, Benton; Mahaffy, Paul R.; Achilles, Cherie; Wray, James J.; Gellert, Ralf; Yen, Albert; Blake, David F.; Vaniman, David T.; Glavin, Daniel P.; Eigenbrode, Jennifer L.; Trainer, Melissa G.; Navarro-González, Rafael; McKay, Christopher P.; Freissinet, Caroline; Martin, Peter

2017-10-01

Of 15 samples analyzed to date, the Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) has detected oxychlorine compounds (perchlorate or chlorate) in 12 samples. The presence of oxychlorine species is inferred from the release of oxygen at temperatures <600 °C and HCl between 350-850 °C when a sample is heated to 850 °C. The O2 release temperature varies with sample, likely caused by different cations, grain size differences, or catalytic effects of other minerals. In the oxychlorine-containing samples, perchlorate abundances range from 0.06 ± 0.03 to 1.15 ± 0.5 wt% Cl2O7 equivalent. Comparing these results to the elemental Cl concentration measured by the Alpha Particle X-ray Spectrometer (APXS) instrument, oxychlorine species account for 5-40% of the total Cl present.The variation in oxychlorine abundance has implications for their production and preservation over time. For example, the John Klein (JK) and Cumberland (CB) samples were acquired within a few meters of each other and CB contained ~1.2 wt% Cl2O7 equivalent while JK had ~0.1 wt%. One difference between the two samples is that JK has a large number of veins visible in the drill hole wall, indicating more post-deposition alteration and removal.Finally, despite Cl concentrations similar to previous samples, the last three Murray formation samples (Oudam, Marimba, and Quela) had no detectable oxygen released during pyrolysis. This could be a result of oxygen reacting with other species in the sample during pyrolysis. Lab work has shown this is likely to have occurred in SAM but it is unlikely to have consumed all the O2 released. Another explanation is that the Cl is present as chlorides, which is consistent with data from the ChemCam (Chemical Camera) and CheMin (Chemistry and Mineralogy) instruments on MSL. For example, the Quela sample has ~1 wt% elemental Cl detected by APXS, had no detectable O2 released, and halite (NaCl) has been tentatively identified in CheMin X-ray diffraction data.These data show that oxychlorines are likely globally distributed on Mars but the distribution is heterogenous depending on the perchlorate formation mechanism (production rate), burial, and subsequent diagenesis.

Experimental studies of Cl-atom reactions at high temperatures: Cl + H{sub 2} {yields} HCl + H from 291 to 1283 K

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adusei, G.Y.; Fontijn, A.

1994-12-31

A method is presented for producing Cl atoms for kinetic experiments above 750 K. Combined with a low temperature Cl-atom production technique, rate coefficients for the title reaction have been obtained over a wide temperature range. The Cl atoms were generated by flash photolysis of CCl{sub 4} for the low-temperature measurements and by pulsed laser photolysis of NaCl for the high-temperature measurements. The relative Cl-atom concentrations were monitored by time-resolved resonance fluorescence. The data are well fitted by the expression k{sub 1}(291--1,283 K) = 4.4 {times} 10{sup {minus}11} exp({minus}2568 K/T) cm{sup 3}/molecule, with 2{sigma} precision limits of {+-} 9 {+-}16more » %, depending on temperature, and corresponding 2{sigma} accuracy limits of about {+-} 26 %. There is good agreement between the rate coefficients measured here and those from previous low-temperature studies, leading to the recommendation k{sub 1}(200--1,283 K) = 2.3 {times} 10{sup {minus}16} (T/K){sup 1.63} exp({minus}1592 K/T) cm{sup 3}/molecule s, with a suggested 2{sigma} accuracy limit of {+-}28% for the combined data. A transition state theory calculation base don a semiempirical London-Eyring-Polanyi-Sato (LEPS) potential energy surface gives excellent agreement with the combined experimental results. Extension of their previous recommendation for the reverse reaction to lower temperatures leads to k{sub 2}(200--1,200 K) = 6.6 {times} 10{sup {minus}16} (T/K){sup 1.44} exp({minus}1241 K/T) cm{sup 3}/molecule s, with 2{sigma} accuracy limits within {+-}25 %. There is excellent agreement between the present data and the predicted expression from that reaction and equilibrium data.« less

Long-lived crowded-litter mice exhibit lasting effects on insulin sensitivity and energy homeostasis.

PubMed

Sadagurski, Marianna; Landeryou, Taylor; Blandino-Rosano, Manuel; Cady, Gillian; Elghazi, Lynda; Meister, Daniel; See, Lauren; Bartke, Andrzej; Bernal-Mizrachi, Ernesto; Miller, Richard A

2014-06-01

The action of nutrients on early postnatal growth can influence mammalian aging and longevity. Recent work has demonstrated that limiting nutrient availability in the first 3 wk of life [by increasing the number of pups in the crowded-litter (CL) model] leads to extension of mean and maximal lifespan in genetically normal mice. In this study, we aimed to characterize the impact of early-life nutrient intervention on glucose metabolism and energy homeostasis in CL mice. In our study, we used mice from litters supplemented to 12 or 15 pups and compared those to control litters limited to eight pups. At weaning and then throughout adult life, CL mice are significantly leaner and consume more oxygen relative to control mice. At 6 mo of age, CL mice had low fasting leptin concentrations, and low-dose leptin injections reduced body weight and food intake more in CL female mice than in controls. At 22 mo, CL female mice also have smaller adipocytes compared with controls. Glucose and insulin tolerance tests show an increase in insulin sensitivity in 6 mo old CL male mice, and females become more insulin sensitive later in life. Furthermore, β-cell mass was significantly reduced in the CL male mice and was associated with reduction in β-cell proliferation rate in these mice. Together, these data show that early-life nutrient intervention has a significant lifelong effect on metabolic characteristics that may contribute to the increased lifespan of CL mice.

Circumstellar chlorine chemistry and a search for AlCl

NASA Astrophysics Data System (ADS)

Clegg, R. E. S.; Wootten, H. A.

1980-09-01

The J = 7-6 transition of AlCl has been sought in carbon-rich circumstellar shells, Orion A, and Sgr B-2. The upper limit for IRC + 10216 is 20 times less than the predicted value for fully associated AlCl. It is suggested that either the initial density in the circumstellar gas flow (not greater than 10 to the 10th per cu cm) or the gaseous Al and Cl are depleted by grains in this object.

Constant Enthalpy Change Value during Pyrophosphate Hydrolysis within the Physiological Limits of NaCl*

PubMed Central

Wakai, Satoshi; Kidokoro, Shun-ichi; Masaki, Kazuo; Nakasone, Kaoru; Sambongi, Yoshihiro

2013-01-01

A decrease in water activity was thought to result in smaller enthalpy change values during PPi hydrolysis, indicating the importance of solvation for the reaction. However, the physiological significance of this phenomenon is unknown. Here, we combined biochemistry and calorimetry to solve this problem using NaCl, a physiologically occurring water activity-reducing reagent. The pyrophosphatase activities of extremely halophilic Haloarcula japonica, which can grow at ∼4 m NaCl, and non-halophilic Escherichia coli and Saccharomyces cerevisiae were maximal at 2.0 and 0.1 m NaCl, respectively. Thus, halophilic and non-halophilic pyrophosphatases exhibit distinct maximal activities at different NaCl concentration ranges. Upon calorimetry, the same exothermic enthalpy change of −35 kJ/mol was obtained for the halophile and non-halophiles at 1.5–4.0 and 0.1–2.0 m NaCl, respectively. These results show that solvation changes caused by up to 4.0 m NaCl (water activity of ∼0.84) do not affect the enthalpy change in PPi hydrolysis. It has been postulated that PPi is an ATP analog, having a so-called high energy phosphate bond, and that the hydrolysis of both compounds is enthalpically driven. Therefore, our results indicate that the hydrolysis of high energy phosphate compounds, which are responsible for biological energy conversion, is enthalpically driven within the physiological limits of NaCl. PMID:23965994

Cytoskeletal confinement of CX3CL1 limits its susceptibility to proteolytic cleavage by ADAM10.

PubMed

Wong, Harikesh S; Jaumouillé, Valentin; Heit, Bryan; Doodnauth, Sasha A; Patel, Sajedabanu; Huang, Yi-Wei; Grinstein, Sergio; Robinson, Lisa A

2014-12-01

CX3CL1 is a unique chemokine that acts both as a transmembrane endothelial adhesion molecule and, upon proteolytic cleavage, a soluble chemoattractant for circulating leukocytes. The constitutive release of soluble CX3CL1 requires the interaction of its transmembrane species with the integral membrane metalloprotease ADAM10, yet the mechanisms governing this process remain elusive. Using single-particle tracking and subdiffraction imaging, we studied how ADAM10 interacts with CX3CL1. We observed that the majority of cell surface CX3CL1 diffused within restricted confinement regions structured by the cortical actin cytoskeleton. These confinement regions sequestered CX3CL1 from ADAM10, precluding their association. Disruption of the actin cytoskeleton reduced CX3CL1 confinement and increased CX3CL1-ADAM10 interactions, promoting the release of soluble chemokine. Our results demonstrate a novel role for the cytoskeleton in limiting membrane protein proteolysis, thereby regulating both cell surface levels and the release of soluble ligand. © 2014 Wong et al. This article is distributed by The American Society for Cell Biology under license from the author(s). Two months after publication it is available to the public under an Attribution–Noncommercial–Share Alike 3.0 Unported Creative Commons License (http://creativecommons.org/licenses/by-nc-sa/3.0).

Statistical Requirements For Pass-Fail Testing Of Contraband Detection Systems

NASA Astrophysics Data System (ADS)

Gilliam, David M.

2011-06-01

Contraband detection systems for homeland security applications are typically tested for probability of detection (PD) and probability of false alarm (PFA) using pass-fail testing protocols. Test protocols usually require specified values for PD and PFA to be demonstrated at a specified level of statistical confidence CL. Based on a recent more theoretical treatment of this subject [1], this summary reviews the definition of CL and provides formulas and spreadsheet functions for constructing tables of general test requirements and for determining the minimum number of tests required. The formulas and tables in this article may be generally applied to many other applications of pass-fail testing, in addition to testing of contraband detection systems.

THE K-REGION DIHYDRODIOL OF BENZO[A]PYRENE INDUCES DNA DAMAGE AND MORPHOLOGICAL CELL TRANSFORMATION IN C3H10T1/2CL8 MOUSE EMBRYO CELLS WITHOUT THE FORMATION OF DETECTABLE STABLE COVALENT DNA ADDUCTS

EPA Science Inventory

The K -region dihydrodiol ofbenzo[ a ]pyrene induces DNA damage and morphological cell transformation in C3HlOTY2CL8 mouse embryo cells without the formation of detectable stable covalent DNA adducts

Benzo[ a ]pyrene (B[ a ]P) is the most thoroughly studied polycyclic aro...

Five-Year Wilkinson Microwave Anisotropy Probe Observations: Data Processing, Sky Maps, and Basic Results

NASA Technical Reports Server (NTRS)

Hinshaw, G.; Weiland, J. L.; Hill, R. S.; Odegard, N.; Larson, D.; Bennett, C. L.; Dunkley, J.; Gold, B.; Greason, M. R.; Jarosik, N.;

Five-Year Wilkinson Microwave Anisotropy Probe Observations: Data Processing, Sky Maps, and Basic Results

NASA Astrophysics Data System (ADS)

Hinshaw, G.; Weiland, J. L.; Hill, R. S.; Odegard, N.; Larson, D.; Bennett, C. L.; Dunkley, J.; Gold, B.; Greason, M. R.; Jarosik, N.; Komatsu, E.; Nolta, M. R.; Page, L.; Spergel, D. N.; Wollack, E.; Halpern, M.; Kogut, A.; Limon, M.; Meyer, S. S.; Tucker, G. S.; Wright, E. L.

2009-02-01

We present new full-sky temperature and polarization maps in five frequency bands from 23 to 94 GHz, based on data from the first five years of the Wilkinson Microwave Anisotropy Probe (WMAP) sky survey. The new maps are consistent with previous maps and are more sensitive. The five-year maps incorporate several improvements in data processing made possible by the additional years of data and by a more complete analysis of the instrument calibration and in-flight beam response. We present several new tests for systematic errors in the polarization data and conclude that W-band polarization data is not yet suitable for cosmological studies, but we suggest directions for further study. We do find that Ka-band data is suitable for use; in conjunction with the additional years of data, the addition of Ka band to the previously used Q- and V-band channels significantly reduces the uncertainty in the optical depth parameter, τ. Further scientific results from the five-year data analysis are presented in six companion papers and are summarized in Section 7 of this paper. With the five-year WMAP data, we detect no convincing deviations from the minimal six-parameter ΛCDM model: a flat universe dominated by a cosmological constant, with adiabatic and nearly scale-invariant Gaussian fluctuations. Using WMAP data combined with measurements of Type Ia supernovae and Baryon Acoustic Oscillations in the galaxy distribution, we find (68% CL uncertainties): Ω b h 2 = 0.02267+0.00058 -0.00059, Ω c h 2 = 0.1131 ± 0.0034, ΩΛ = 0.726 ± 0.015, ns = 0.960 ± 0.013, τ = 0.084 ± 0.016, and Δ_{R}^2 = (2.445± 0.096)× 10^{-9} at k = 0.002 Mpc-1. From these we derive σ8 = 0.812 ± 0.026, H 0 = 70.5 ± 1.3 km s-1 Mpc-1, Ω b = 0.0456 ± 0.0015, Ω c = 0.228 ± 0.013, Ω m h 2 = 0.1358+0.0037 -0.0036, z reion = 10.9 ± 1.4, and t 0 = 13.72 ± 0.12 Gyr. The new limit on the tensor-to-scalar ratio is r < 0.22(95%CL), while the evidence for a running spectral index is insignificant, dns /dln k = -0.028 ± 0.020 (68% CL). We obtain tight, simultaneous limits on the (constant) dark energy equation of state and the spatial curvature of the universe: -0.14 < 1 + w < 0.12(95%CL) and -0.0179 < Ω k < 0.0081(95%CL). The number of relativistic degrees of freedom, expressed in units of the effective number of neutrino species, is found to be N eff = 4.4 ± 1.5 (68% CL), consistent with the standard value of 3.04. Models with N eff = 0 are disfavored at >99.5% confidence. Finally, new limits on physically motivated primordial non-Gaussianity parameters are -9 < f local NL < 111 (95% CL) and -151 < f equil NL < 253 (95% CL) for the local and equilateral models, respectively. WMAP is the result of a partnership between Princeton University and NASA's Goddard Space Flight Center. Scientific guidance is provided by the WMAP Science Team.

Melting of the precipitated ice IV in LiCl aqueous solution and polyamorphism of water.

PubMed

Mishima, Osamu

2011-12-08

Melting of the precipitated ice IV in supercooled LiCl-H(2)O solution was studied in the range of 0-0.6 MPa and 160-270 K. Emulsified solution was used to detect this metastable transition. Ice IV was precipitated from the aqueous solution of 2.0 mol % LiCl (or 4.8 mol % LiCl) in each emulsion particle at low-temperature and high-pressure conditions, and the emulsion was decompressed at different temperatures. The melting of ice IV was detected from the temperature change of the emulsified sample during the decompression. There was an apparently sudden change in the slope of the ice IV melting curve (liquidus) in the pressure-temperature diagram. At the high-pressure and high-temperature side of the change, the solute-induced freezing point depression was observed. At the low-pressure and low-temperature side, ice IV transformed into ice Ih on the decompression, and the transition was almost unrelated to the concentration of LiCl. These experimental results were roughly explained by the presumed existence of two kinds of liquid water (low-density liquid water and high-density liquid water), or polyamorphism in water, and by the simple assumption that LiCl dissolved maily in high-density liquid water. © 2011 American Chemical Society

Effects of cations and anions as aggregating agents on SERS detection of cotinine (COT) and trans-3'-hydroxycotinine (3HC).

PubMed

Han, Sungyub; Hong, Seongmin; Li, Xiao

2013-11-15

The sensitivity of surface-enhanced Raman spectroscopy (SERS) highly depends on experimental factors including aggregating agents and pH. Using silver nanoparticles as the substrate, the effect of five cationic (K(+), Na(+), Mg(2+), Li(+), Ca(2+)) and three anionic (Cl(-), Br(-), I(-)) aggregating agents was examined on the SERS detection of tobacco-related biomarkers, namely cotinine (COT) and trans-3'-hydroxycotinine (3HC). The optimal concentrations of the aggregating agents with respect to highest SERS intensity varied widely (from 1.5 mM for MgCl2 to 150 mM for LiCl). Both cations and anions strongly influenced the SERS enhancement. When Cl(-) was used as the anion, Mg(2+) and Na(+) exhibited the highest SERS intensities for COT and 3HC, respectively. When Mg(2+) was used as the cation, Cl(-) and Br(-) generated the highest SERS enhancement for COT and 3HC, respectively. Clearly, SERS enhancement also depended on the target molecule. Among the 11 aggregating agent combinations tested, the highest SERS enhancement is obtained using 1.5 mM MgCl2 for COT at pH 7.0 and 50 mM NaBr for 3HC at pH 3.0. Copyright © 2013 Elsevier Inc. All rights reserved.

Determination of chloride in brazilian crude oils by ion chromatography after extraction induced by emulsion breaking.

PubMed

Robaina, Nicolle F; Feiteira, Fernanda N; Cassella, Alessandra R; Cassella, Ricardo J

2016-08-05

The present paper reports on the development of a novel extraction induced by emulsion breaking (EIEB) method for the determination of chloride in crude oils. The proposed method was based on the formation and breaking of oil-in-water emulsions with the samples and the consequential transference of the highly water-soluble chloride to the aqueous phase during emulsion breaking, which was achieved by centrifugation. The determination of chloride in the extracts was performed by ion chromatography (IC) with conductivity detection. Several parameters (oil phase:aqueous phase ratio, crude oil:mineral oil ratio, shaking time and type and concentration of surfactant) that could affect the performance of the method were evaluated. Total extraction of chloride from samples could be achieved when 1.0g of oil phase (0.5g of sample+0.5g of mineral oil) was emulsified in 5mL of a 2.5% (m/v) solution of Triton X-114. The obtained emulsion was shaken for 60min and broken by centrifugation for 5min at 5000rpm. The separated aqueous phase was collected, filtered and diluted before analysis by IC. Under these conditions, the limit of detection was 0.5μgg(-1) NaCl and the limit of quantification was 1.6μgg(-1) NaCl. We applied the method to the determination of chloride in six Brazilian crude oils and the results did not differ statistically from those obtained by the ASTM D6470 method when the paired Student-t-test, at 95% confidence level, was applied. Copyright © 2016 Elsevier B.V. All rights reserved.

An electrochemical sulfite biosensor based on gold coated magnetic nanoparticles modified gold electrode.

PubMed

Rawal, Rachna; Chawla, Sheetal; Pundir, Chandra Shekhar

2012-01-15

A sulfite oxidase (SO(X)) (EC 1.8.3.1) purified from Syzygium cumini leaves was immobilized onto carboxylated gold coated magnetic nanoparticles (Fe(3)O(4)@GNPs) electrodeposited onto the surface of a gold (Au) electrode through N-ethyl-N'-(3-dimethylaminopropyl) carbodiimide (EDC)-N-hydroxy succinimide (NHS) chemistry. An amperometric sulfite biosensor was fabricated using SO(X)/Fe(3)O(4)@GNPs/Au electrode as working electrode, Ag/AgCl as standard and Pt wire as auxiliary electrode. The working electrode was characterized by Fourier Transform Infrared (FTIR) Spectroscopy, Cyclic Voltammetry (CV), Scanning Electron Microscopy (SEM) and Electrochemical Impedance Spectroscopy (EIS) before and after immobilization of SO(X). The biosensor showed optimum response within 2s when operated at 0.2V (vs. Ag/AgCl) in 0.1 M Tris-HCl buffer, pH 8.5 and at 35 °C. Linear range and detection limit were 0.50-1000 μM and 0.15 μM (S/N=3) respectively. Biosensor was evaluated with 96.46% recovery of added sulfite in red wine and 1.7% and 3.3% within and between batch coefficients of variation respectively. Biosensor measured sulfite level in red and white wines. There was good correlation (r=0.99) between red wines sulfite value by standard DTNB (5,5'-dithio-bis-(2-nitrobenzoic acid)) method and the present method. Enzyme electrode was used 300 times over a period of 4 months, when stored at 4 °C. Biosensor has advantages over earlier biosensors that it has excellent electrocatalysis towards sulfite, lower detection limit, higher storage stability and no interference by ascorbate, cysteine, fructose and ethanol. Copyright © 2011 Elsevier B.V. All rights reserved.

Accurate determination of non-metallic impurities in high purity tetramethylammonium hydroxide using inductively coupled plasma tandem mass spectrometry

NASA Astrophysics Data System (ADS)

Fu, Liang; Xie, Hualin; Shi, Shuyun; Chen, Xiaoqing

2018-06-01

The content of non-metallic impurities in high-purity tetramethylammonium hydroxide (HPTMAH) aqueous solution has an important influence on the yield, electrical properties and reliability of the integrated circuit during the process of chip etching and cleaning. Therefore, an efficient analytical method to directly quantify the content of non-metallic impurities in HPTMAH aqueous solutions is necessary. The present study was aimed to develop a novel method that can accurately determine seven non-metallic impurities (B, Si, P, S, Cl, As, and Se) in an aqueous solution of HPTMAH by inductively coupled plasma tandem mass spectrometry (ICP-MS/MS). The samples were measured using a direct injection method. In the MS/MS mode, oxygen and hydrogen were used as reaction gases in the octopole reaction system (ORS) to eliminate mass spectral interferences during the analytical process. The detection limits of B, Si, P, S, Cl, As, and Se were 0.31, 0.48, 0.051, 0.27, 3.10, 0.008, and 0.005 μg L-1, respectively. The samples were analyzed by the developed method and the sector field inductively coupled plasma mass spectrometry (SF-ICP-MS) was used for contrastive analysis. The values of these seven elements measured using ICP-MS/MS were consistent with those measured by SF-ICP-MS. The proposed method can be utilized to analyze non-metallic impurities in HPTMAH aqueous solution. Table S2 Multiple potential interferences on the analytes. Table S3 Parameters of calibration curve and the detection limit (DL). Table S4 Results obtained for 25% concentration high-purity grade TMAH aqueous solution samples (μg L-1, mean ± standard deviation, n = 10).

Formation of chlorinated lipids post-chlorine gas exposure

PubMed Central

Ford, David A.; Honavar, Jaideep; Albert, Carolyn J.; Duerr, Mark A.; Oh, Joo Yeun; Doran, Stephen; Matalon, Sadis; Patel, Rakesh P.

2016-01-01

Exposure to chlorine (Cl2) gas can occur during accidents and intentional release scenarios. However, biomarkers that specifically indicate Cl2 exposure and Cl2-derived products that mediate postexposure toxicity remain unclear. We hypothesized that chlorinated lipids (Cl-lipids) formed by direct reactions between Cl2 gas and plasmalogens serve as both biomarkers and mediators of post-Cl2 gas exposure toxicities. The 2-chloropalmitaldehyde (2-Cl-Pald), 2-chlorostearaldehyde (2-Cl-Sald), and their oxidized products, free- and esterified 2-chloropalmitic acid (2-Cl-PA) and 2-chlorostearic acid were detected in the lungs and plasma of mouse and rat models of Cl2 gas exposure. Levels of Cl-lipids were highest immediately post-Cl2 gas exposure, and then declined over 72 h with levels remaining 20- to 30-fold higher at 24 h compared with baseline. Glutathione adducts of 2-Cl-Pald and 2-Cl-Sald also increased with levels peaking at 4 h in plasma. Notably, 3-chlorotyrosine also increased after Cl2 gas exposure, but returned to baseline within 24 h. Intranasal administration of 2-Cl-PA or 2-Cl-Pald at doses similar to those formed in the lung after Cl2 gas exposure led to increased distal lung permeability and inflammation and systemic endothelial dysfunction characterized by loss of eNOS-dependent vasodilation. These data suggest that Cl-lipids could serve as biomarkers and mediators for Cl2 gas exposure and toxicity. PMID:27324796

Formation of chlorinated lipids post-chlorine gas exposure.

PubMed

Ford, David A; Honavar, Jaideep; Albert, Carolyn J; Duerr, Mark A; Oh, Joo Yeun; Doran, Stephen; Matalon, Sadis; Patel, Rakesh P

2016-08-01

Exposure to chlorine (Cl2) gas can occur during accidents and intentional release scenarios. However, biomarkers that specifically indicate Cl2 exposure and Cl2-derived products that mediate postexposure toxicity remain unclear. We hypothesized that chlorinated lipids (Cl-lipids) formed by direct reactions between Cl2 gas and plasmalogens serve as both biomarkers and mediators of post-Cl2 gas exposure toxicities. The 2-chloropalmitaldehyde (2-Cl-Pald), 2-chlorostearaldehyde (2-Cl-Sald), and their oxidized products, free- and esterified 2-chloropalmitic acid (2-Cl-PA) and 2-chlorostearic acid were detected in the lungs and plasma of mouse and rat models of Cl2 gas exposure. Levels of Cl-lipids were highest immediately post-Cl2 gas exposure, and then declined over 72 h with levels remaining 20- to 30-fold higher at 24 h compared with baseline. Glutathione adducts of 2-Cl-Pald and 2-Cl-Sald also increased with levels peaking at 4 h in plasma. Notably, 3-chlorotyrosine also increased after Cl2 gas exposure, but returned to baseline within 24 h. Intranasal administration of 2-Cl-PA or 2-Cl-Pald at doses similar to those formed in the lung after Cl2 gas exposure led to increased distal lung permeability and inflammation and systemic endothelial dysfunction characterized by loss of eNOS-dependent vasodilation. These data suggest that Cl-lipids could serve as biomarkers and mediators for Cl2 gas exposure and toxicity. Copyright © 2016 by the American Society for Biochemistry and Molecular Biology, Inc.

A re-evaluation of laser heterodyne radiometer ClO measurements. [for stratospheric chemistry studies

NASA Technical Reports Server (NTRS)

Menzies, R. T.

1983-01-01

Previously reported measurements of stratospheric ClO using a balloon-borne laser heterodyne radiometer, launched from Palestine, Texas, are re-evaluated as a result of recent spectroscopic data. A spectral feature which was observed during September, 1978 and November, 1979 flights was incorrectly identified as a ClO absorption line, while a second feature observed during the latter flight with somewhat limited sensitivity is now believed to be due to ClO. This new interpretation results in a measured ClO profile which falls off more rapidly with decreasing altitude than the previous results indicated.

Ultraviolet spectrum and chemical reactivity of the ClO dimer

NASA Technical Reports Server (NTRS)

Demore, W. B.; Tschuikow-Roux, E.

1990-01-01

The ClO dimer was prepared by photolysis (wavelength greater than 300 nm) of Cl2/Cl2O or Cl2/O3 mixtures or by photolysis of Cl2O alone. Temperatures were in the range 195-217 K, and experiments were carried out both in the gas phase and in the cryogenic solvents CF4, CO2, and N2O. Dimer cross sections in the range 190-400 nm are reported both in the gas phase and in the solvents. Results indicate that ClOOCl is the only dimer structure formed as a stable product. Upper limits of 1 x 10 to the -19th and 1 x 10 to the -20th cu cm/s are placed on the reactions of ClOOCl with O3 and with itself, respectively.

Study of the surface-enhanced Raman spectroscopy of residual impurities in hydroxylamine-reduced silver colloid and the effects of anions on the colloid activity.

PubMed

Dong, Xiao; Gu, Huaimin; Liu, Fangfang

2012-03-01

The paper investigated the residual ions in hydroxylamine-reduced silver colloid (HRSC) and the relationship between the condition of HRSC and the enhanced mechanisms of this colloid. We also detected the SERS of MB and studied the effects of anions on the Raman signal. In the case of HRSC, the bands of residual ions diminish while the bands of Ag-anions increase gradually with increasing the concentrations of Cl(-) and NO(3)(-). It means the affinity of residual ions on the silver surface is weaker than that of Cl(-) and NO(3)(-) and the residual ions are replaced gradually by the added Cl(-) or NO(3)(-). The Raman signal of residual ions can be detected by treatment with anions that do not bind strongly to the silver surface, such as SO(4)(2-). The most intense band of Ag-anions bonds can be also observed when adding weakly binding anions to the colloid. However, the anions which make up the Ag-anions bonds are residual Cl(-) and the effect of weakly binding anions is only to aggregate the silver particles. Residual Cl(-) can be replaced by I(-) which has the highest affinity. From the detection of methylene blue (MB), the effects of anions on the enhancement of Raman signal are discussed in detail, and these findings could make the conditions suitable for detecting analytes in high efficiency. This study will have a profound implication to SERS users about their interpretation of SERS spectra when obtaining these anomalous bands. Copyright © 2011 Elsevier B.V. All rights reserved.

Laser flash photolysis studies of atmospheric free radical chemistry using optical diagnostic techniques

NASA Technical Reports Server (NTRS)

Wine, Paul H.; Nicovich, J. M.; Hynes, Anthony J.; Stickel, Robert E.; Thorn, R. P.; Chin, Mian; Cronkhite, Jeffrey A.; Shackelford, Christie J.; Zhao, Zhizhong; Daykin, Edward P.

1993-01-01

Some recent studies carried out in our laboratory are described where laser flash photolytic production of reactant free radicals has been combined with reactant and/or product detection using time-resolved optical techniques to investigate the kinetics and mechanisms of important atmospheric chemical reactions. Discussed are (1) a study of the radical-radical reaction O + BrO yields Br + O2 where two photolysis lasers are employed to prepare the reaction mixture and where the reactants O and BrO are monitored simultaneously using atomic resonance fluorescence to detect O and multipass UV absorption to detect BrO; (2) a study of the reaction of atomic chlorine with dimethylsulfide (CH3SCH3) where atomic resonance fluorescence detection of Cl is employed to elucidate the kinetics and tunable diode laser absorption spectroscopy is employed to investigate the HCl product yield; and (3) a study of the aqueous phase chemistry of Cl2(-) radicals where longpath UV absorption spectroscopy is employed to investigate the kinetics of the Cl2(-) + H2O reaction.

Psychophysical Models for Signal Detection with Time Varying Uncertainty. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Gai, E.

1975-01-01

Psychophysical models for the behavior of the human operator in detection tasks which include change in detectability, correlation between observations and deferred decisions are developed. Classical Signal Detection Theory (SDT) is discussed and its emphasis on the sensory processes is contrasted to decision strategies. The analysis of decision strategies utilizes detection tasks with time varying signal strength. The classical theory is modified to include such tasks and several optimal decision strategies are explored. Two methods of classifying strategies are suggested. The first method is similar to the analysis of ROC curves, while the second is based on the relation between the criterion level (CL) and the detectability. Experiments to verify the analysis of tasks with changes of signal strength are designed. The results show that subjects are aware of changes in detectability and tend to use strategies that involve changes in the CL's.

Dynamics of the reactions of O(1D) with HCl, DCl, and Cl2

NASA Astrophysics Data System (ADS)

Matsumi, Yutaka; Tonokura, Kenichi; Kawasaki, Masahiro; Tsuji, Kazuhide; Obi, Kinichi

1993-05-01

The reactions O(1D)+HCl→OH+Cl (1a) and OCl+H (1b), O(1D)+DCl→OD+Cl (2a) and OCl+D (2b), and O(1D)+Cl2→OCl+Cl (3) are studied at an average collision energy of 7.6, 7.7, and 8.8 kcal/mol for (1), (2), and (3), respectively. H, D, and Cl atoms are detected by the resonance-enhanced multiphoton ionization technique. The average kinetic energies released to the products are estimated from Doppler profile measurements of the product atoms. The relative yields [OCl+H]/[OH+Cl] and [OCl+D]/[OD+Cl] are directly measured, and a strong isotope effect (H/D) on the relative yields is found. The fine-structure branding ratios [Cl(2P1/2]/[Cl(2P3/2)] of the reaction products are also measured. The results suggest that nonadiabatic couplings take place at the exit channels of the reactions (1a) and (2a), while the reaction (3) is totally adiabatic.

Revisiting the SOLVE ClOOCl and ClO measurements in consideration of the Pope et al., 2007 results.

NASA Astrophysics Data System (ADS)

Stimpfle, R. M.; Wilmouth, D. M.; Anderson, J. G.

2008-12-01

The interpretation of the SOLVE measurements of ClOOCl and ClO has recently acquired renewed interest with the publication of new ClOOCl cross section measurements (Pope et al, 2007) that are significantly smaller than expected. The SOLVE analysis showed agreement with J values based upon the JPL 2002 or Burkholder 1990 cross sections, dependent upon various values for the rate constant for dimer production. J values based upon Pope are currently not in agreement with the SOLVE observations and/or their analysis. As various hypotheses emerge to possibly rationalize the Pope results, it is worthwhile to consider two critical constraints that the SOLVE halogen data place on any newly considered Clx photochemistry. The first constraint is the lack of a detectable Cl atom signal in the observed background signal at the temperature used for thermal dissociation of ClOOCl. The second constraint is the observed SZA dependence of the partitioning of ClO and ClOOCl. Here we present evidence of the Cl atom constraint.

Using multiple PCR and CE with chemiluminescence detection for simultaneous qualitative and quantitative analysis of genetically modified organism.

PubMed

Guo, Longhua; Qiu, Bin; Chi, Yuwu; Chen, Guonan

2008-09-01

In this paper, an ultrasensitive CE-CL detection system coupled with a novel double-on-column coaxial flow detection interface was developed for the detection of PCR products. A reliable procedure based on this system had been demonstrated for qualitative and quantitative analysis of genetically modified organism-the detection of Roundup Ready Soy (RRS) samples was presented as an example. The promoter, terminator, function and two reference genes of RRS were amplified with multiplex PCR simultaneously. After that, the multiplex PCR products were labeled with acridinium ester at the 5'-terminal through an amino modification and then analyzed by the proposed CE-CL system. Reproducibility of analysis times and peak heights for the CE-CL analysis were determined to be better than 0.91 and 3.07% (RSD, n=15), respectively, for three consecutive days. It was shown that this method could accurately and qualitatively detect RRS standards and the simulative samples. The evaluation in terms of quantitative analysis of RRS provided by this new method was confirmed by comparing our assay results with those of the standard real-time quantitative PCR (RT-QPCR) using SYBR Green I dyes. The results showed a good coherence between the two methods. This approach demonstrated the possibility for accurate qualitative and quantitative detection of GM plants in a single run.

Reanalysis of the Viking results suggests perchlorate and organics at mid-latitudes on Mars

NASA Astrophysics Data System (ADS)

Navarro-Gonzalez, R.; Vargas, E.; de La Rosa, J.; Raga, A. C.; McKay, C.

2010-12-01

The most comprehensive search for organics in the Martian soil was performed by the Viking Landers. Martian soil was subjected to a thermal volatilization process in order to vaporize and break organic molecules, and the resultant gases and volatiles were analyzed by gas chromatography-mass spectrometry. Only water at 0.1-1.0 wt% was detected with traces of chloromethane at 15 ppb in the Viking Landing site 1, and water at 0.05-1.0 wt% and carbon dioxide at 50-700 ppm with traces of dichloromethane at 0.04-40 ppb in the Viking Landing site 2. The abundance ratio of the 35Cl and 37Cl isotopes in these chlorohydrocarbons was 3:1, corresponding to the terrestrial isotopic abundance. Therefore, these chlorohydrocarbons were considered to be terrestrial contaminants although they had not been detected at those levels in the blank runs. Recently, perchlorate was discovered in the Martian Arctic soil by the Phoenix Lander. Here we show that when Mars-like soils from the Atacama Desert with 32±6 ppm of organic carbon are mixed with 1 wt% magnesium perchlorate and heated nearly all the organics present are decomposed to water and carbon dioxide, but a small amount are chlorinated forming 1.6 ppm of chloromethane and 0.02 ppm of dichloromethane at 500○C. A chemical kinetics model was developed to predict the degree of oxidation and chlorination of organics in the Viking oven. The isotopic distribution of 35Cl and 37Cl for Mars is not known. Studies on Earth indicate that there is no isotopic fractionation of chlorine in the mantle or crust, despite the fact that it is significantly depleted on the planet as compare to solar abundances. The 37Cl/35Cl isotopic ratio in carbonaceous chondrites is similar to the Earth’s value, which suggests that the terrestrial planets, including Mars, were all formed from a similar reservoir of chlorine species in the presolar nebulae and that there was no further isotopic fractionation during the Earth’s differentiation or late accretion of volatiles. Consequently, 37Cl/35Cl ratio should be the same on Mars as well as on the Earth. Re-interpretation of the Viking results therefore suggests ≤0.1% perchlorate and 1.5-6.5 ppm organic carbon at the landing site 1, and ≤0.1% perchlorate and 0.7-2.6 ppm organic carbon at the landing site 2. The detection of organics on Mars is important to assess locations for future experiments to detect life itself. We suggest that future missions to Mars should include life detection experiments.

Atmospheric chlorinated polyfluorinated ether sulfonate and ionic perfluoroalkyl acids in 2006 to 2014 in Dalian, China.

PubMed

Liu, Wei; Qin, Hui; Li, Jingwen; Zhang, Qian; Zhang, Huanhuan; Wang, Zaoshi; He, Xin

2017-10-01

Chlorinated polyfluorinated ether sulfonate (Cl-PFESA; trade name F-53B) is an alternative product for perfluorooctane sulfonate (PFOS) used in metal plating; little is known about its levels in the environment and its risks. To our knowledge, the present study constitutes the first report of Cl-PFESA in the atmosphere. In 2006 to 2014, C8 Cl-PFESA, along with ionic perfluoroalkyl acids (PFAAs), was detected in atmospheric particulate matter in Dalian, China. Concentrations of C8 Cl-PFESA increased from 140 pg/m 3 in 2007 to 722 pg/m 3 in 2014. Levels of 11 (total) ionic PFAAs increased in 2006 to 2008 and decreased afterward, with a range of 35.7 to 860 pg/m 3 . The PFAAs in the particulate matter were dominated by perfluorocarboxylates, with perfluorooctanoate detected at the highest concentration at a mean level of 71.7 pg/m 3 , followed by perfluoroheptanoate and perfluorohexanoate. Perfluorosulfonates were detected at lower levels, with mean concentrations of PFOS, perfluorobutanesulfonate, and perfluorohexane sulfonate of 5.73, 1.64, and 1.24 pg/m 3 , respectively. Back-trajectory analysis suggested that the air mass approaching Dalian during the sampling originated from the northwest, where fluorochemical industry parks and metal plating industries are densely located. No significant correlation was observed between Cl-PFESA and the ionic PFAAs. The relatively high Cl-PFESA concentrations suggested that it possibly contributed largely to the previously reported exposure to undefined organic fluorine compounds, for which further research on emission and environmental risks is needed. Environ Toxicol Chem 2017;36:2581-2586. © 2017 SETAC. © 2017 SETAC.

Selenium-binding protein 1: a sensitive urinary biomarker to detect heavy metal-induced nephrotoxicity.

PubMed

Lee, Eui Kyung; Shin, Young-Jun; Park, Eun Young; Kim, Nam Deuk; Moon, Aree; Kwack, Seung Jun; Son, Ji Yeon; Kacew, Sam; Lee, Byung Mu; Bae, Ok-Nam; Kim, Hyung Sik

2017-04-01

Identifying novel biomarkers to detect nephrotoxicity is clinically important. Here, we attempted to identify new biomarkers for mercury-induced nephrotoxicity and compared their sensitivity to that of traditional biomarkers in animal models. Comparative proteomics analysis was performed in kidney tissues of Sprague-Dawley rats after oral treatment with HgCl 2 (0.1, 1, or 5 mg/kg/day) for 21 days. Kidney cortex tissues were analyzed by two-dimensional gel electrophoresis/matrix-assisted laser desorption/ionization, and differentially expressed proteins were identified. The corresponding spots were quantitated by RT-PCR. Selenium-binding protein 1 (SBP1) was found to be the most markedly upregulated protein in the kidney cortex of rats after HgCl 2 administration. However, blood urea nitrogen, serum creatinine, and glucose levels increased significantly only in the 1 or 5 mg/kg HgCl 2 -treated groups. A number of urinary excretion proteins, including kidney injury molecule-1, clusterin, monocyte chemoattractant protein-1, and β-microglobulin, increased dose-dependently. Histopathological examination revealed severe proximal tubular damage in high-dose (5 mg/kg) HgCl 2 -exposed groups. In addition, urinary excretion of SBP1 significantly increased in a dose-dependent manner. To confirm the critical role of SBP1 as a biomarker for nephrotoxicity, normal kidney proximal tubular cells were treated with HgCl 2 , CdCl 2 , or cisplatin for 24 h. SBP1 levels significantly increased in conditioned media exposed to nephrotoxicants, but decreased in cell lysates. Our investigations suggest that SBP1 may play a critical role in the pathological processes underlying chemical-induced nephrotoxicity. Thus, urinary excretion of SBP1 might be a sensitive and specific biomarker to detect early stages of kidney injury.

Simple and scalable growth of AgCl nanorods by plasma-assisted strain relaxation on flexible polymer substrates

NASA Astrophysics Data System (ADS)

Park, Jae Yong; Lee, Illhwan; Ham, Juyoung; Gim, Seungo; Lee, Jong-Lam

2017-06-01

Implementing nanostructures on plastic film is indispensable for highly efficient flexible optoelectronic devices. However, due to the thermal and chemical fragility of plastic, nanostructuring approaches are limited to indirect transfer with low throughput. Here, we fabricate single-crystal AgCl nanorods by using a Cl2 plasma on Ag-coated polyimide. Cl radicals react with Ag to form AgCl nanorods. The AgCl is subjected to compressive strain at its interface with the Ag film because of the larger lattice constant of AgCl compared to Ag. To minimize strain energy, the AgCl nanorods grow in the [200] direction. The epitaxial relationship between AgCl (200) and Ag (111) induces a strain, which leads to a strain gradient at the periphery of AgCl nanorods. The gradient causes a strain-induced diffusion of Ag atoms to accelerate the nanorod growth. Nanorods grown for 45 s exhibit superior haze up to 100% and luminance of optical device increased by up to 33%.

Biodegradation of the High Explosive Hexanitrohexaazaiso-wurtzitane (CL-20)

PubMed Central

Karakaya, Pelin; Christodoulatos, Christos; Koutsospyros, Agamemnon; Balas, Wendy; Nicolich, Steve; Sidhoum, Mohammed

2009-01-01

The aerobic biodegradability of the high explosive CL-20 by activated sludge and the white rot fungus Phanerochaete chrysosporium has been investigated. Although activated sludge is not effective in degrading CL-20 directly, it can mineralize the alkaline hydrolysis products. Phanerochaete chrysosporium degrades CL-20 in the presence of supplementary carbon and nitrogen sources. Biodegradation studies were conducted using various nutrient media under diverse conditions. Variables included the CL-20 concentration; levels of carbon (as glycerol) and ammonium sulfate and yeast extract as sources of nitrogen. Cultures that received CL-20 at the time of inoculation transformed CL-20 completely under all nutrient conditions studied. When CL-20 was added to pre-grown cultures, degradation was limited. The extent of mineralization was monitored by the 14CO2 time evolution; up to 51% mineralization was achieved when the fungus was incubated with [14C]-CL-20. The kinetics of CL-20 biodegradation by Phanerochaete chrysosporium follows the logistic kinetic growth model. PMID:19440524

Biodegradation of the high explosive hexanitrohexaazaiso-wurtzitane (CL-20).

PubMed

Karakaya, Pelin; Christodoulatos, Christos; Koutsospyros, Agamemnon; Balas, Wendy; Nicolich, Steve; Sidhoum, Mohammed

2009-04-01

The aerobic biodegradability of the high explosive CL-20 by activated sludge and the white rot fungus Phanerochaete chrysosporium has been investigated. Although activated sludge is not effective in degrading CL-20 directly, it can mineralize the alkaline hydrolysis products. Phanerochaete chrysosporium degrades CL-20 in the presence of supplementary carbon and nitrogen sources. Biodegradation studies were conducted using various nutrient media under diverse conditions. Variables included the CL-20 concentration; levels of carbon (as glycerol) and ammonium sulfate and yeast extract as sources of nitrogen. Cultures that received CL-20 at the time of inoculation transformed CL-20 completely under all nutrient conditions studied. When CL-20 was added to pre-grown cultures, degradation was limited. The extent of mineralization was monitored by the (14)CO(2) time evolution; up to 51% mineralization was achieved when the fungus was incubated with [(14)C]-CL-20. The kinetics of CL-20 biodegradation by Phanerochaete chrysosporium follows the logistic kinetic growth model.

Evolution of chemically processed air parcels in the lower stratosphere

NASA Technical Reports Server (NTRS)

Stolarski, Richard S.; Douglass, Anne R.; Schoeberl, Mark R.

1994-01-01

Aircraft, ground-based, and satellite measurements indicate large concentrations of ClO in the lower stratosphere in and near the polar vortex. The amount of local ozone depletion caused by these large ClO concentrations will depend on the relative rates of ozone loss and ClO recovery. ClO recovery occurs when NO(x), from HNO3 photolysis, reacts with ClO to form ClONO2. We show that air parcels with large amounts of ClO will experience a subsequent ozone depletion that depends on the solar zenith angle. When the solar zenith angle is large in the middle of winter, the recovery of the ClO concentration in the parcel is slow relative to ozone depletion. In the spring, when the solar zenith angle is smaller, the ClO recovery is much faster. After ClO recovery, the chlorine chemistry has not returned to normal. The ClO has been converted to ClONO2. ClO production from further encounters with PSCs will be limited by the heterogeneous reaction of ClONO2 with water. Large ozone depletions, of the type seen in the Antarctic, occur only if there is significant irreversible denitrification in the air parcel.

T-Cell-Mediated Immune Responses in Patients with Cutaneous or Mucosal Leishmaniasis: Long-Term Evaluation after Therapy

PubMed Central

Da-Cruz, Alda Maria; Bittar, Rita; Mattos, Marise; Oliveira-Neto, Manuel P.; Nogueira, Ricardo; Pinho-Ribeiro, Vanessa; Azeredo-Coutinho, Rilza Beatriz; Coutinho, Sergio G.

2002-01-01

T-cell immune responses in patients with cutaneous leishmaniasis (CL) and mucosal leishmaniasis (ML) were studied during the active disease, at the end of therapy, and 1 to 17 years posttherapy (long-term follow-up). Lymphocyte proliferative responses, phenotypic characterization of CD4+ and CD8+ Leishmania-reactive T cells, and cytokine production were assayed. Patients with active ML and CL showed higher proportions of CD4+ than CD8+ T cells. In CL, the healing process was associated with a decrease of CD4+ and an increase of CD8+, leading to similar CD4+ and CD8+ proportions. This pattern was only seen in ML after long-term therapy. Long-term follow-up of patients with CL showed a positive CD4+/CD8+ ratio as observed during the active disease, although the percentages of these T cell subsets were significantly lower. Patients with CL did not show significant differences between gamma interferon (IFN-γ) and interleukin-5 (IL-5) production during the period of study. Patients with active ML presented higher IFN-γ and IL-5 levels compared to patients with active CL. IL-4 was only detected during active disease. Patients long term after cure from ML showed increasing production of IFN-γ, significant decrease of IL-5, and no IL-4 production. Two apparently beneficial immunological parameters were detected in tegumentary leishmaniasis: (i) decreasing proportions of CD4+ Leishmania-reactive T cells in the absence of IL-4 production associated with cure of CL and ML and (ii) decreasing levels of IL-5 long after cure, better detected in patients with ML. The observed T-cell responses maintained for a long period in healed patients could be relevant for immunoprotection against reinfection and used as a parameter for determining the prognosis of patients and selecting future vaccine preparations. PMID:11874860

Critical limits for the control points for halal poultry slaughter.

PubMed

Shahdan, Intan Azura; Regenstein, Joe Mac; Rahman, Mohammad Tariqur

2017-06-01

This study proposes critical limits (CL) for control points for halal slaughter (CPHS). Previously, 6 control points (CP) were determined, and CL for these 6 CPHS are suggested based on: 1) a literature survey for the CL for CP 1 (poultry breeding, rearing, and poultry feed) and CP 2 (welfare of poultry during transportation and lairage); 2) a field survey of slaughter plants in Kuantan (Malaysia) for CP 3 (immobilization), CP 4 (slaughter), CP 5 (time for full bleed-out), and CP 6 (washing and packaging); and 3) controlled experiments to refine the CL for CP 3, 4, and 5. The CL for CP 1 focused on stress reduction during rearing and use of substances that could compromise poultry meat wholesomeness. The CL for CP 2 emphasizes humane best-practices for handling poultry during lairage. The CL for CP 3 suggests a gap of 5 s between 2 shackles if only one shackler is employed and shackling times of <1 min for live chickens. In countries permitting water-bath electrical stunning of halal poultry, the stunning current needed to induce unconsciousness must be defined for the breed and bird size but not cause any chicken deaths. The CL for CP 4 mandates the recitation of the tasmiyah (the invocation), which if done for every chicken, will require ≥5 s between stunning and neck cutting. The CL for CP 4 also includes information about the slaughter knife. In CP 5 the recommended minimum time between neck cutting and scalding is 9.5 min. Finally, the CL for CP 6 emphasizes good supply chain hygiene and zero adulteration from haram species and substances. © 2016 Poultry Science Association Inc.

Cl/Br ratios and chlorine isotope evidences for groundwater salinization and its impact on groundwater arsenic, fluoride and iodine enrichment in the Datong basin, China.

PubMed

Li, Junxia; Wang, Yanxin; Xie, Xianjun

2016-02-15

In order to identify the salinization processes and its impact on arsenic, fluoride and iodine enrichment in groundwater, hydrogeochemical and environmental isotope studies have been conducted on groundwater from the Datong basin, China. The total dissolved solid (TDS) concentrations in groundwater ranged from 451 to 8250 mg/L, and 41% of all samples were identified as moderately saline groundwater with TDS of 3000-10,000 mg/L. The results of groundwater Cl concentrations, Cl/Br molar ratio and Cl isotope composition suggest that three processes including water-rock interaction, surface saline soil flushing, and evapotranspiration result in the groundwater salinization in the study area. The relatively higher Cl/Br molar ratio in groundwater from multiple screening wells indicates the contribution of halite dissolution from saline soil flushed by vertical infiltration to the groundwater salinization. However, the results of groundwater Cl/Br molar ratio model indicate that the effect of saline soil flushing practice is limited to account for the observed salinity variation in groundwater. The plots of groundwater Cl vs. Cl/Br molar ratio, and Cl vs δ(37)Cl perform the dominant effects of evapotranspiration on groundwater salinization. Inverse geochemical modeling results show that evapotranspiration may cause approximately 66% loss of shallow groundwater to account for the observed hydrochemical pattern. Due to the redox condition fluctuation induced by irrigation activities and evapotranspiration, groundwater salinization processes have negative effects on groundwater arsenic enrichment. For groundwater iodine and fluoride enrichment, evapotranspiration partly accounts for their elevation in slightly saline water. However, too strong evapotranspiration would restrict groundwater fluoride concentration due to the limitation of fluorite solubility. Copyright © 2015. Published by Elsevier B.V.

Au-Pt-Au nanoraspberry structures used for mercury ion detection

NASA Astrophysics Data System (ADS)

Huang, Jiang-Hao; Huang, Shuai; Wen, Xiaoyan; Li, Min; Lu, Haifei

2017-12-01

Detection of Hg2+ with high sensitivity is of great significance in the biochemical sensing field. Quantitative of Hg2+ was realized based on the influence of Hg2+ on the UV-vis absorption performance of Au-Pt-Au core-shell nanoraspberry (APA)-rhodamine-6G (R6G) structure. First, APA sol was added into R6G indicator solution and the UV-vis absorption signal intensity of R6G was evidently promoted. The signal intensity monotonously increased as more APA sol was added. However, when HgCl2 solution was introduced, the signal intensity declined. A linear relationship between Hg2+ concentration and signal intensity at 527 nm was revealed, based on which quantitative determination of Hg2+ could be realized. Hg2+ detection sensitivity was measured to be 0.031 a.u./M with a limit of detection of 10-7 M and the response time was 20 s. A high Hg2+ detection selectivity over Cu2+, Na+, Li+, and K+ was demonstrated. Due to its simplicity and high sensitivity, the proposed method could find an extensive application prospect in the Hg2+ detection field.

Application of NaClO-treated multiwalled carbon nanotubes as solid phase extraction sorbents for preconcentration of trace 2,4-dichlorophenoxyacetic acid in aqueous samples.

PubMed

Lu, Ping; Deng, Dayi; Ni, Xiaodan

2012-09-01

Multiwalled carbon nanotubes functionalized by oxidation of original multiwalled carbon nanotubes with NaClO were prepared and their application as solid phase extraction sorbent for 2,4-dichlorophenoxyacetic acid (2,4-D) was investigated systemically, and a new method was developed for the determination of trace 2,4-D in water samples based on extraction and preconcentration of 2,4-D with solid phase extraction columns packed with NaClO-treated multiwalled carbon nanotubes prior to its determination by HPLC. The optimum experimental parameters for preconcentration of 2,4-D, including the column activating conditions, the amount of the sorbent, pH of the sample, elution composition, and elution volume, were investigated. The results indicated 2,4-D could be quantitatively retained by 100 mg NaClO-treated multiwalled carbon nanotubes at pH 5, and then eluted completely with 10 mL 3:1 (v/v) methanol-ammonium acetate solution (0.3 mol/L). The detection limit of this method for 2,4-D was 0.15 μg/L, and the relative standard deviation was 2.3% for fortified tap water samples and 2.5% for fortified riverine water sample at the 10 μg/L level. The method was validated using fortified tap water and riverine water samples with known amount of 2,4-D at the 0.4, 10, and 30 μg/L levels, respectively. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.