The development of optimized high performance liquid chromatography systems for the analysis of improvised explosives

Existing instrumental techniques must be adaptable to the analysis of novel explosives if science is to keep up with the practices of terrorists and criminals. The focus of this work has been the development of analytical techniques for the analysis of two types of novel explosives: ascorbic acid-based propellants, and improvised mixtures of concentrated hydrogen peroxide/fuel. In recent years, the use of these explosives in improvised explosive devices (IEDs) has increased. It is therefore important to develop methods which permit the identification of the nature of the original explosive from post-blast residues. Ascorbic acid-based propellants are low explosives which employ an ascorbic acid fuel source with a nitrate/perchlorate oxidizer. A method which utilized ion chromatography with indirect photometric detection was optimized for the analysis of intact propellants. Post-burn and post-blast residues if these propellants were analyzed. It was determined that the ascorbic acid fuel and nitrate oxidizer could be detected in intact propellants, as well as in the post-burn and post-blast residues. Degradation products of the nitrate and perchlorate oxidizers were also detected. With a quadrupole time-of-flight mass spectrometer (QToFMS), exact mass measurements are possible. When an HPLC instrument is coupled to a QToFMS, the combination of retention time with accurate mass measurements, mass spectral fragmentation information, and isotopic abundance patterns allows for the unequivocal identification of a target analyte. An optimized HPLC-ESI-QToFMS method was applied to the analysis of ascorbic acid-based propellants. Exact mass measurements were collected for the fuel and oxidizer anions, and their degradation products. Ascorbic acid was detected in the intact samples and half of the propellants subjected to open burning; the intact fuel molecule was not detected in any of the post-blast residue. Two methods were optimized for the analysis of trace levels of hydrogen peroxide: HPLC with fluorescence detection (HPLC-FD), and HPLC with electrochemical detection (HPLC-ED). Both techniques were extremely selective for hydrogen peroxide. Both methods were applied to the analysis of post-blast debris from improvised mixtures of concentrated hydrogen peroxide/fuel; hydrogen peroxide was detected on variety of substrates. Hydrogen peroxide was detected in the post-blast residues of the improvised explosives TATP and HMTD.

The Development of High Performance Liquid Chromatography Systems for the Analysis of Improvised Explosives

Existing instrumental techniques must be adaptable to the analysis of novel explosives if science is to keep up with the practices of terrorists and criminals. The focus of this work has been the development of analytical techniques for the analysis of two types of novel explosives: ascorbic acid-based propellants, and improvised mixtures of concentrated hydrogen peroxide/fuel. In recent years, the use of these explosives in improvised explosive devices (IEDs) has increased. It is therefore important to develop methods which permit the identification of the nature of the original explosive from post-blast residues. Ascorbic acid-based propellants are low explosives which employ an ascorbic acid fuel source with a nitrate/perchlorate oxidizer. A method which utilized ion chromatography with indirect photometric detection was optimized for the analysis of intact propellants. Post-burn and post-blast residues if these propellants were analyzed. It was determined that the ascorbic acid fuel and nitrate oxidizer could be detected in intact propellants, as well as in the post-burn and post-blast residues. Degradation products of the nitrate and perchlorate oxidizers were also detected. With a quadrupole time-of-flight mass spectrometer (QToFMS), exact mass measurements are possible. When an HPLC instrument is coupled to a QToFMS, the combination of retention time with accurate mass measurements, mass spectral fragmentation information, and isotopic abundance patterns allows for the unequivocal identification of a target analyte. An optimized HPLC-ESI-QToFMS method was applied to the analysis of ascorbic acid-based propellants. Exact mass measurements were collected for the fuel and oxidizer anions, and their degradation products. Ascorbic acid was detected in the intact samples and half of the propellants subjected to open burning; the intact fuel molecule was not detected in any of the post-blast residue. Two methods were optimized for the analysis of trace levels of hydrogen peroxide: HPLC with fluorescence detection (HPLC-FD), and HPLC with electrochemical detection (HPLC-ED). Both techniques were extremely selective for hydrogen peroxide. Both methods were applied to the analysis of post-blast debris from improvised mixtures of concentrated hydrogen peroxide/fuel; hydrogen peroxide was detected on variety of substrates. Hydrogen peroxide was detected in the post-blast residues of the improvised explosives TATP and HMTD.

Social support, risk, and adjustment of immigrant preadolescents

The current study was designed to explore the salience of social support, immigrant status, and risk in middle childhood and early adolescence across two time periods as indicated by measures of school adjustment and well-being. Participants included 691 children of public elementary schools in grades 4 and 6 who were interviewed in 1997 (Time 1) and reinterviewed two years later (Time 2); 539 were U.S.-born, and 152 were foreign-born. ^ Repeated measures multivariate analyses of variance (MANOVA's) were conducted to assess the effects of immigrant status and risk on total support, well-being, and school adjustment from Time 1 to Time 2. Follow-up analyses, including Student-Newman-Keuls post hoc tests, were used to test the significance of the differences among the means of support categories (low and high), immigrant status (U.S. born and non-U.S. born), risk (low and high) and time (time 1 and time 2). ^ Results showed that immigrant participants in the high risk group reported significantly lower levels of support than their peers. Further, children of low risk at Time 2 indicated the highest levels of support. Second, immigrant preadolescents, preadolescents who reported low levels of social support, and preadolescents of the high risk reported lower levels of emotional well-being. There was also an interaction of support by risk by time, indicating that children who are at risk and had low levels of social support reported more emotional problems at Time 1. Finally, preadolescents who are at risk and preadolescents who reported lower levels of support were more likely to show school adaptation problems. Findings from this study highlight the importance of a multivariable approach to the study of support, emotional adjustment, and academic adjustment of immigrant preadolescents. ^

Optimization of wireless power transfer via magnetic resonance in different media

A wide range of non-destructive testing (NDT) methods for the monitoring the health of concrete structure has been studied for several years. The recent rapid evolution of wireless sensor network (WSN) technologies has resulted in the development of sensing elements that can be embedded in concrete, to monitor the health of infrastructure, collect and report valuable related data. The monitoring system can potentially decrease the high installation time and reduce maintenance cost associated with wired monitoring systems. The monitoring sensors need to operate for a long period of time, but sensors batteries have a finite life span. Hence, novel wireless powering methods must be devised. The optimization of wireless power transfer via Strongly Coupled Magnetic Resonance (SCMR) to sensors embedded in concrete is studied here. First, we analytically derive the optimal geometric parameters for transmission of power in the air. This specifically leads to the identification of the local and global optimization parameters and conditions, it was validated through electromagnetic simulations. Second, the optimum conditions were employed in the model for propagation of energy through plain and reinforced concrete at different humidity conditions, and frequencies with extended Debye's model. This analysis leads to the conclusion that SCMR can be used to efficiently power sensors in plain and reinforced concrete at different humidity levels and depth, also validated through electromagnetic simulations. The optimization of wireless power transmission via SMCR to Wearable and Implantable Medical Device (WIMD) are also explored. The optimum conditions from the analytics were used in the model for propagation of energy through different human tissues. This analysis shows that SCMR can be used to efficiently transfer power to sensors in human tissue without overheating through electromagnetic simulations, as excessive power might result in overheating of the tissue. Standard SCMR is sensitive to misalignment; both 2-loops and 3-loops SCMR with misalignment-insensitive performances are presented. The power transfer efficiencies above 50% was achieved over the complete misalignment range of 0°-90° and dramatically better than typical SCMR with efficiencies less than 10% in extreme misalignment topologies.

Multifunctional nanoparticles in cancer: In vitro characterization, in vivo distribution, and cellular response after laser-NIR dye-induced heating

A novel biocompatible and biodegradable polymer, termed poly(Glycerol malate co-dodecanedioate) (PGMD), was prepared by thermal condensation method and used for fabrication of nanoparticles (NPs). PGMD NPs were prepared using the single oil emulsion technique and loaded with an imaging/hyperthermia agent (IR820) and a chemotherapeutic agent (doxorubicin, DOX). The size of the void PGMD NPs, IR820-PGMD NPs and DOX-IR820-PGMD NPs were approximately 90 nm, 110 nm, and 125 nm respectively. An acidic environment (pH=5.0) induced higher DOX and IR820 release compared to pH=7.4. DOX release was also enhanced by exposure to laser, which increased the temperature to 42°C. Cytotoxicity of DOX-IR820-PGMD NPs was comparable in MES-SA but was higher in Dx5 cells compared to free DOX plus IR820 (p<0.05). The combination of hyperthermia (HT) and chemotherapy improved cytotoxicity in both cell lines. We also explored the cellular response after rapid, short-term and low thermal dose (laser/Dye/NP) induced-heating, and compared it to slow, long-term and high thermal dose cell incubator heating by investigating the reactive oxygen species (ROS) level, hypoxia-inducible factor-1&agr; (HIF-1&agr;) and vascular endothelial growth factor (VEGF) expression. The cytotoxicity of IR820-PGMD NPs after laser/Dye/NP HT resulted in higher cancer cell killing compared to incubator HT. ROS level, HIF-1&agr; and VEGF expression were elevated under incubator HT, while maintained at the baseline level under the laser/Dye/NP HT. In vivo mouse studies showed that NP formulation significantly improved the plasma half-life of IR820 after tail vein injection. Significant lower IR820 content was observed in kidney in DOX-IR820-PGMD NP treatment as compared to free IR820 treatment in our biodistribution studies (p<0.05). In conclusion, both IR820-PGMD NPs and DOX-IR820-PGMD NPs were successfully developed and used for both imaging and therapeutic purposes. Rapid and short-term laser/Dye/NP HT, with a low thermal dose, did not up-regulate HIF-1&agr; and VEGF expression, whereas slow and long-term incubator HT, with a high thermal dose, can enhance expression of both HIF-1&agr; and VEGF.^

Optimization of Wireless Power Transfer via Magnetic Resonance in Different Media

A wide range of non-destructive testing (NDT) methods for the monitoring the health of concrete structure has been studied for several years. The recent rapid evolution of wireless sensor network (WSN) technologies has resulted in the development of sensing elements that can be embedded in concrete, to monitor the health of infrastructure, collect and report valuable related data. The monitoring system can potentially decrease the high installation time and reduce maintenance cost associated with wired monitoring systems. The monitoring sensors need to operate for a long period of time, but sensors batteries have a finite life span. Hence, novel wireless powering methods must be devised. The optimization of wireless power transfer via Strongly Coupled Magnetic Resonance (SCMR) to sensors embedded in concrete is studied here. First, we analytically derive the optimal geometric parameters for transmission of power in the air. This specifically leads to the identification of the local and global optimization parameters and conditions, it was validated through electromagnetic simulations. Second, the optimum conditions were employed in the model for propagation of energy through plain and reinforced concrete at different humidity conditions, and frequencies with extended Debye's model. This analysis leads to the conclusion that SCMR can be used to efficiently power sensors in plain and reinforced concrete at different humidity levels and depth, also validated through electromagnetic simulations. The optimization of wireless power transmission via SMCR to Wearable and Implantable Medical Device (WIMD) are also explored. The optimum conditions from the analytics were used in the model for propagation of energy through different human tissues. This analysis shows that SCMR can be used to efficiently transfer power to sensors in human tissue without overheating through electromagnetic simulations, as excessive power might result in overheating of the tissue. Standard SCMR is sensitive to misalignment; both 2-loops and 3-loops SCMR with misalignment-insensitive performances are presented. The power transfer efficiencies above 50% was achieved over the complete misalignment range of 0°-90° and dramatically better than typical SCMR with efficiencies less than 10% in extreme misalignment topologies.

Carbon nanostructure based electrodes for high efficiency dye sensitized solar cell

Synthesis and functionalization of large-area graphene and its structural, electrical and electrochemical properties has been investigated. First, the graphene films, grown by thermal chemical vapor deposition (CVD), contain three to five atomic layers of graphene, as confirmed by Raman spectroscopy and high-resolution transmission electron microscopy. Furthermore, the graphene film is treated with CF4 reactive-ion plasma to dope fluorine ions into graphene lattice as confirmed by X-ray photoelectron spectroscopy (XPS) and UV-photoemission spectroscopy (UPS). Electrochemical characterization reveals that the catalytic activity of graphene for iodine reduction enhanced with increasing plasma treatment time, which is attributed to increase in catalytic sites of graphene for charge transfer. The fluorinated graphene is characterized as a counter-electrode (CE) in a dye-sensitized solar cell (DSSC) which shows ~ 2.56% photon to electron conversion efficiency with ~11 mAcm−2 current density. Second, the large scale graphene film is covalently functionalized with HNO3 for high efficiency electro-catalytic electrode for DSSC. The XPS and UPS confirm the covalent attachment of C-OH, C(O)OH and NO3- moieties with carbon atoms through sp2-sp3 hybridization and Fermi level shift of graphene occurs under different doping concentrations, respectively. Finally, CoS-implanted graphene (G-CoS) film was prepared using CVD followed by SILAR method. The G-CoS electro-catalytic electrodes are characterized in a DSSC CE and is found to be highly electro-catalytic towards iodine reduction with low charge transfer resistance (Rct ~5.05 Ωcm 2) and high exchange current density (J0~2.50 mAcm -2). The improved performance compared to the pristine graphene is attributed to the increased number of active catalytic sites of G-CoS and highly conducting path of graphene. We also studied the synthesis and characterization of graphene-carbon nanotube (CNT) hybrid film consisting of graphene supported by vertical CNTs on a Si substrate. The hybrid film is inverted and transferred to flexible substrates for its application in flexible electronics, demonstrating a distinguishable variation of electrical conductivity for both tension and compression. Furthermore, both turn-on field and total emission current was found to depend strongly on the bending radius of the film and were found to vary in ranges of 0.8 - 3.1 V/μm and 4.2 - 0.4 mA, respectively.

An evaluation of an intervention strategy for retention and determination of predictors of success for high -risk students in an associate degree nursing program

The purpose of this study was twofold: (1) to evaluate the effect of a specific instructional Intervention, a Nursing Theory Laboratory, on increasing the retention of high risk students in the associate degree nursing program at Miami-Dade Community College in Miami, Florida; and (2) to identify predictors of success of high risk nursing students in this associate degree nursing program.^ Data were collected from the 195 nursing students enrolled in Nursing Fundamentals during the 1985-1987 academic years, and identified as high risk students. Control and experimental groups were selected based on enrollment in the Nursing Theory Laboratory.^ Results were determined by analyzing several cross-tabulations of selected variables and yielding chi square values, t-tests, and two discriminant analyses. There was no significant relationship between age or ethnic background and enrollment in the Nursing Theory Laboratory. There was no significant relationship between enrollment in the Nursing Theory Laboratory and success in Nursing 1 (Nursing Fundamentals). There was a significant relationship between enrollment in the Nursing Theory Laboratory and success in Nursing 3 (Medical-Surgical Nursing). Writing assessment test scores in two entrance tests and high risk categories, based on the number of enrollments in required science courses, were identified as predictors of success in this program.^ The conclusion was that the Nursing Theory Laboratory does not significantly improve retention of high risk associate degree nursing students if they are enrolled in this intervention at the same time they are enrolled in Nursing Fundamentals. Since those students who were enrolled in the Nursing Theory Laboratory had a significantly higher success rate in Nursing 3, than those students who were not enrolled in the Nursing Theory Laboratory, a recommendation of this study was to offer the Nursing Theory Laboratory to high risk students prior to the beginning of nursing courses. Another recommendation was that students deficient in reading and writing skills should be required to enroll in developmental courses prior to enrollment in the nursing course. ^

Retention and special education referral practices before and after the implementation of high -stakes testing

The rewards and sanctions associated with high-stakes testing may induce educators to participate in practices that will ensure the elimination of the scores of low-achieving students from the testing pool. Two ways in which scores may be eliminated is through retention or referral to special education. ^ This study examined the use of these practices at 179 elementary schools in Miami-Dade County Public Schools, the 4th largest school district in the country. Between- and within-subjects designs were analyzed using repeated measures analysis of variance to compare retention and referral to special education practices over a five-year period of time, two years prior to and two years after the implementation of Florida's high-stakes test, the Florida Comprehensive Assessment Test, FCAT. ^ Significant main effects for referral and retention over time were demonstrated. The use of retention steadily increased over the first three years, with its usage maintained during the fourth year. While the use of referral actually decreased from the first to second years, a significant change occurred after the implementation of the FCAT. ^ Examination of the use of these practices according to student and school characteristics revealed significant differences. Increases in the use of referral across time was significant for Black, non-Hispanic and Hispanic students, all limited English proficiency population categories, medium and low socioeconomic status category schools, all grade levels, and for schools with accountability grades of A. C, D and F with the most striking absolute increase occurring for F schools. Increases in the use of retention across time were significant for all ethnic groups, limited English proficiency categories, and socioeconomic status categories, for grades kindergarten through four and by gender. Significant increases occurred for schools with accountability performance grades of C, D and F; however the most dramatic increase occurred for the F schools. A direct relationship between performance category grade of school and their use of retention was demonstrated. The results suggest that schools changed their use of referral and retention in response to the implementation of the FCAT. ^

Retention and special education referral practices before and after the implementation of high-stakes testing

The rewards and sanctions associated with high-stakes testing may induce educators to participate in practices that will ensure the elimination of the scores of low-achieving students from the testing pool. Two ways in which scores may be eliminated is through retention or referral to special education. This study examined the use of these practices at 179 elementary schools in Miami-Dade County Public Schools, the 4th largest school district in the country. Between- and within-subjects designs were analyzed using repeated measures analysis of variance to compare retention and referral to special education practices over a five-year period of time, two years prior to and two years after the implementation of Florida's high-stakes test, the Florida Comprehensive Assessment Test, FCAT. Significant main effects for referral and retention over time were demonstrated. The use of retention steadily increased over the first three years, with its usage maintained during the fourth year. While the use of referral actually decreased from the first to second years, a significant change occurred after the implementation of the FCAT. Examination of the use of these practices according to student and school characteristics revealed significant differences. Increases in the use of referral across time was significant for Black, non-Hispanic and Hispanic students, all limited English proficiency population categories, medium and low socioeconomic status category schools, all grade levels, and for schools with accountability grades of A, C, D and F with the most striking absolute increase occurring for F schools. Increases in the use of retention across time were significant for all ethnic groups, limited English proficiency categories, and socioeconomic status categories, for grades kindergarten through four and by gender. Significant increases occurred for schools with accountability performance grades of C, D and F; however the most dramatic increase occurred for the F schools. A direct relationship between performance category grade of school and their use of retention was demonstrated. The results suggest that schools changed their use of referral and retention in response to the implementation of the FCAT.