Silicon quantum dots embedded in a SiO2 matrix: From structural study to carrier transport properties

We study the details of electronic transport related to the atomistic structure of silicon quantum dots embedded in a silicon dioxide matrix using ab initio calculations of the density of states. Several structural and composition features of quantum dots (QDs), such as diameter and amorphization level, are studied and correlated with transport under transfer Hamiltonian formalism. The current is strongly dependent on the QD density of states and on the conduction gap, both dependent on the dot diameter. In particular, as size increases, the available states inside the QD increase, while the QD band gap decreases due to relaxation of quantum confinement. Both effects contribute to increasing the current with the dot size. Besides, valence band offset between the band edges of the QD and the silica, and conduction band offset in a minor grade, increases with the QD diameter up to the theoretical value corresponding to planar heterostructures, thus decreasing the tunneling transmission probability and hence the total current. We discuss the influence of these parameters on electron and hole transport, evidencing a correlation between the electron (hole) barrier value and the electron (hole) current, and obtaining a general enhancement of the electron (hole) transport for larger (smaller) QD. Finally, we show that crystalline and amorphous structures exhibit enhanced probability of hole and electron current, respectively.

Analytical interference of 4-hydroxy-3-methoxymethamphetamine with the measurement of plasma free normetanephrine by ultra-high pressure liquid chromatography-tandem mass spectrometry.

OBJECTIVES: The diagnosis of pheochromocytoma relies on the measurement of plasma free metanephrines assay whose reliability has been considerably improved by ultra-high pressure liquid chromatography tandem mass spectrometry (UHPLC-MS/MS). Here we report an analytical interference occurring between 4-hydroxy-3-methoxymethamphetamine (HMMA), a metabolite of 3,4-methylenedioxymethamphetamine (MDMA, "Ecstasy"), and normetanephrine (NMN) since they share a common pharmacophore resulting in the same product ion after fragmentation. DESIGN AND METHODS: Synthetic HMMA was spiked into plasma samples containing various concentrations of NMN and the intensity of the interference was determined by UPLC-MS/MS before and after improvement of the analytical method. RESULTS: Using a careful adjustment of chromatographic conditions including the change of the UPLC analytical column, we were able to distinguish both compounds. HMMA interference for NMN determination should be seriously considered since MDMA activates the sympathetic nervous system and if confounded with NMN may lead to false-positive tests when performing a differential diagnostic of pheochromocytoma.

Performance Analysis of Two Quantum Reaction Dynamics Codes: Time-Dependent and Time-Independent Strategies

The computer simulation of reaction dynamics has nowadays reached a remarkable degree of accuracy. Triatomic elementary reactions are rigorously studied with great detail on a straightforward basis using a considerable variety of Quantum Dynamics computational tools available to the scientific community. In our contribution we compare the performance of two quantum scattering codes in the computation of reaction cross sections of a triatomic benchmark reaction such as the gas phase reaction Ne + H2+ %12. NeH++ H. The computational codes are selected as representative of time-dependent (Real Wave Packet [ ]) and time-independent (ABC [ ]) methodologies. The main conclusion to be drawn from our study is that both strategies are, to a great extent, not competing but rather complementary. While time-dependent calculations advantages with respect to the energy range that can be covered in a single simulation, time-independent approaches offer much more detailed information from each single energy calculation. Further details such as the calculation of reactivity at very low collision energies or the computational effort related to account for the Coriolis couplings are analyzed in this paper.

Evaluation of Long-Term Field Performance of Cold In-Place Recycled Roads: Field and Laboratory Testing, TR-502, 2007

Cold in-place recycling (CIR) has become an attractive method for rehabilitating asphalt roads that have good subgrade support and are suffering distress related to non-structural aging and cracking of the pavement layer. Although CIR is widely used, its use could be expanded if its performance were more predictable. Transportation officials have observed roads that were recycled under similar circumstances perform very differently for no clear reason. Moreover, a rational mix design has not yet been developed, design assumptions regarding the structural support of the CIR layer remain empirical and conservative, and there is no clear understanding of the cause-effect relationships between the choices made during the design/construction process and the resulting performance. The objective of this project is to investigate these relationships, especially concerning the age of the recycled pavement, cumulative traffic volume, support conditions, aged engineering properties of the CIR materials, and road performance. Twenty-four CIR asphalt roads constructed in Iowa from 1986 to 2004 were studied: 18 were selected from a sample of roads studied in a previous research project (HR-392), and 6 were selected from newer CIR projects constructed after 1999. This report describes the results of comprehensive field and laboratory testing for these CIR asphalt roads. The results indicate that the modulus of the CIR layer and the air voids of the CIR asphalt binder were the most important factors affecting CIR pavement performance for high-traffic roads. For low-traffic roads, the wet indirect tensile strength significantly affected pavement performance. The results of this research can help identify changes that should be made with regard to design, material selection, and construction in order to improve the performance and cost-effectiveness of future recycled roads.

Evaluation of Long-Term Field Performance of Cold In-Place Recycled Roads: Summary Report, TR-502, 2007

Cold in-place recycling (CIR) has become an attractive method for rehabilitating asphalt roads that have good subgrade support and are suffering distress related to non-structural aging and cracking of the pavement layer. Although CIR is widely used, its use could be expanded if its performance were more predictable. Transportation officials have observed roads that were recycled under similar circumstances perform very differently for no clear reason. Moreover, a rational mix design has not yet been developed, design assumptions regarding the structural support of the CIR layer remain empirical and conservative, and there is no clear understanding of the cause-effect relationships between the choices made during the design/construction process and the resulting performance. The objective of this project is to investigate these relationships, especially concerning the age of the recycled pavement, cumulative traffic volume, support conditions, aged engineering properties of the CIR materials, and road performance. Twenty-four CIR asphalt roads constructed in Iowa from 1986 to 2004 were studied: 18 were selected from a sample of roads studied in a previous research project (HR-392), and 6 were selected from newer CIR projects constructed after 1999. This report summarizes the results of a comprehensive program of field distress surveys, field testing, and laboratory testing for these CIR asphalt roads. The results of this research can help identify changes that should be made with regard to design, material selection, and construction in order to lengthen the time between rehabilitation cycles and improve the performance and cost-effectiveness of future recycled roads.

Design, Construction, and Field Testing of an Ultra High Performance Concrete Pi-Girder Bridge, TR-574, 2011

Among the variety of road users and vehicle types that travel on U.S. public roadways, slow moving vehicles (SMVs) present unique safety and operations issues. SMVs include vehicles that do not maintain a constant speed of 25 mph, such as large farm equipment, construction vehicles, or horse-drawn buggies. Though the number of crashes involving SMVs is relatively small, SMV crashes tend to be severe. Additionally, SMVs can be encountered regularly on non-Interstate/non-expressway public roadways, but motorists may not be accustomed to these vehicles. This project was designed to improve transportation safety for SMVs on Iowa’s public roadway system. This report includes a literature review that shows various SMV statistics and laws across the United States, a crash study based on three years of Iowa SMV crash data, and recommendations from the SMV community.

Manual of Laboratory Mix Design Procedure for Cold In-Place Recycling using Foamed Asphalt (CIR-foam), TR-474, 2007

The objective is to determine the optimum percentage of water needed to produce the best foam properties for a given asphalt binder. The optimum water content is determined by achieving the maximum expansion ratio and half-life of the foamed asphalt. Expansion ratio is defined as the maximum volume over its original volume and half-life is defined as the time in seconds for foam to become a half of its maximum volume.

Examination of Curing Criteria for Cold In-Place Recycling, TR-553, 2008

Cold In-Place Recycling (CIR) has been used widely in rehabilitating the rural highways because it improves a long-term pavement performance. A CIR layer is normally covered by a hot mix asphalt (HMA) overlay in order to protect it from water ingress and traffic abrasion and obtain the required pavement structure and texture. Curing is the term currently used for the period of time that a CIR layer should remain exposed to drying conditions before an HMA overlay is placed. The industry standard for curing time is 10 days to 14 days or a maximum moisture content of 1.5 percent, which appear to be very conservative. When the exposed CIR layer is required to carry traffic for many weeks before the wearing surface is placed, it increases the risk of a premature failure in both CIR layer and overlay. This study was performed to explore technically sound ways to identify minimum in-place CIR properties necessary to permit placement of the HMA overlay. To represent the curing process of CIR pavement in the field construction, three different laboratory curing procedures were examined: 1) uncovered, 2) semi-covered and 3) covered specimens. The indirect tensile strength of specimens in all three curing conditions did not increase during an early stage of curing but increased during a later stage of curing usually when the moisture content falls below 1.5%. Dynamic modulus and flow number increased as curing time increased and moisture contents decreased. For the same curing time, CIR-foam specimens exhibited the higher tensile strength and less moisture content than CIR-emulsion. The laboratory test results concluded that the method of curing temperature and length of the curing period significantly affect the properties of the CIR mixtures. The moisture loss index was developed to predict the moisture condition in the field and, in the future, this index be calibrated with the measurements of temperature and moisture of a CIR layer in the field.

Examination of Curing Criteria for Cold In-Place Recycling Phase 2: Measuring Temperature, Moisture, Deflection and Distress from CIR Test Section, TR-590, 2009

The previous research performed laboratory experiments to measure the impacts of the curing on the indirect tensile strength of both CIR-foam and CIR-emulsion mixtures. However, a fundamental question was raised during the previous research regarding a relationship between the field moisture content and the laboratory moisture content. Therefore, during this research, both temperature and moisture conditions were measured in the field by embedding the sensors at a midpoint and a bottom of the CIR layer. The main objectives of the research are to: (1) measure the moisture levels throughout a CIR layer and (2) develop a moisture loss index to determine the optimum curing time of CIR layer before HMA overlay. To develop a set of moisture loss indices, the moisture contents and temperatures of CIR-foam and CIR-emulsion layers were monitored for five months. Based on the limited field experiment, the following conclusions are derived: 1. The moisture content of the CIR layer can be monitored accurately using the capacitance type moisture sensor. 2. The moisture loss index for CIR layers is a viable tool in determining the optimum timing for an overlay without measuring actual moisture contents. 3. The modulus back-calculated based on the deflection measured by FWD seemed to be in a good agreement with the stiffness measured by geo-gauge. 4. The geo-gauge should be considered for measuring the stiffness of CIR layer that can be used to determine the timing of an overlay. 5. The stiffness of CIR-foam layer increased as a curing time increased and it seemed to be more influenced by a temperature than moisture content. The developed sets of moisture loss indices based on the field measurements will help pavement engineers determine an optimum timing of an overlay without continually measuring moisture conditions in the field using a nuclear gauge.

Examination of Curing Criteria for Cold In-Place Recycling (Phase 3: Calibration of Moisture Loss Indices and Development of Stiffness Gain Model), TR-609, 2011

In the previous study, moisture loss indices were developed based on the field measurements from one CIR-foam and one CIR-emulsion construction sites. To calibrate these moisture loss indices, additional CIR construction sites were monitored using embedded moisture and temperature sensors. In addition, to determine the optimum timing of an HMA overlay on the CIR layer, the potential of using the stiffness of CIR layer measured by geo-gauge instead of the moisture measurement by a nuclear gauge was explored. Based on the monitoring the moisture and stiffness from seven CIR project sites, the following conclusions are derived: 1. In some cases, the in-situ stiffness remained constant and, in other cases, despite some rainfalls, stiffness of the CIR layers steadily increased during the curing time. 2. The stiffness measured by geo-gauge was affected by a significant amount of rainfall. 3. The moisture indices developed for CIR sites can be used for predicting moisture level in a typical CIR project. The initial moisture content and temperature were the most significant factors in predicting the future moisture content in the CIR layer. 4. The stiffness of a CIR layer is an extremely useful tool for contractors to use for timing their HMA overlay. To determine the optimal timing of an HMA overlay, it is recommended that the moisture loss index should be used in conjunction with the stiffness of the CIR layer.

Comparison between a high-resolution single-stage Orbitrap and a triple quadrupole mass spectrometer for quantitative analyses of drugs.

The capabilities of a high-resolution (HR), accurate mass spectrometer (Exactive-MS) operating in full scan MS mode was investigated for the quantitative LC/MS analysis of drugs in patients' plasma samples. A mass resolution of 50,000 (FWHM) at m/z 200 and a mass extracted window of 5 ppm around the theoretical m/z of each analyte were used to construct chromatograms for quantitation. The quantitative performance of the Exactive-MS was compared with that of a triple quadrupole mass spectrometer (TQ-MS), TSQ Quantum Discovery or Quantum Ultra, operating in the conventional selected reaction monitoring (SRM) mode. The study consisted of 17 therapeutic drugs including 8 antifungal agents (anidulafungin, caspofungin, fluconazole, itraconazole, hydroxyitraconazole posaconazole, voriconazole and voriconazole-N-oxide), 4 immunosuppressants (ciclosporine, everolimus, sirolimus and tacrolimus) and 5 protein kinase inhibitors (dasatinib, imatinib, nilotinib, sorafenib and sunitinib). The quantitative results obtained with HR-MS acquisition show comparable detection specificity, assay precision, accuracy, linearity and sensitivity to SRM acquisition. Importantly, HR-MS offers several benefits over TQ-MS technology: absence of SRM optimization, time saving when changing the analysis from one MS to another, more complete information of what is in the samples and easier troubleshooting. Our work demonstrates that U/HPLC coupled to Exactive HR-MS delivers comparable results to TQ-MS in routine quantitative drug analyses. Considering the advantages of HR-MS, these results suggest that, in the near future, there should be a shift in how routine quantitative analyses of small molecules, particularly for therapeutic drugs, are performed.

Casein fractions of ultra high temperature milk with different somatic cell counts

The objective of this work was to evaluate the effect of somatic cell counts (SCC) in casein fractions of ultra high temperature (UHT) milk. Raw milks were categorized in SCC groups of low (200,000-320,000 cells mL-1), intermediate (380,000-560,000 cells mL-1) and high cells (600,000-800,000 cells mL-1). Five replicates of UHT milks within each SCC category were analyzed for casein fractions after 8, 30, 60, 90 and 120 days of storage through high performance liquid chromatography. SCC showed effect only on beta-casein reduction. SCC in raw milk increases the proteolysis of UHT milk, as a consequence of beta-casein degradation.

Modelos para ajuste da produção de gases em silagens de girassol e milho

O objetivo deste trabalho foi identificar entre os modelos Brody, Von Bertalanffy, Gompertz, France, Logístico, Logístico modificado e Logístico bicompartimental, aquele que apresenta maior qualidade de ajuste à curva de produção cumulativa de gases em silagens de girassol e milho. Os critérios adotados foram: coeficiente de determinação, quadrado médio do resíduo, análise gráfica das curvas observadas e estimadas, análise gráfica de dispersão dos resíduos estudentizados, erro percentual médio, eficiência relativa e número de iterações para atingir a convergência. Os modelos Brody, France e Logístico bicompartimental apresentaram os maiores valores de coeficiente de determinação em ambos os substratos, e a diferença entre eles pode ser considerada desprezível. Estes modelos apresentaram, também, os menores valores de quadrado médio do resíduo em silagens de girassol, e a diferença entre eles foi considerada desprezível. Os modelos Brody e France apresentaram menor quadrado médio do resíduo em silagens de milho. Todos os modelos apresentaram dispersão positiva dos resíduos em ambos os substratos após 144 horas de incubação. O modelo Brody apresentou menor erro percentual médio e número de iterações em ambos os substratos. Os modelos Logístico bicompartimental e France apresentaram maior eficiência relativa, respectivamente, em silagens de girassol e milho. Assim, o modelo Logístico bicompartimental apresenta maior qualidade de ajuste à curva de produção de gases em silagens de girassol e milho.

Laser-Ultraviolet-A induced ultra weak photon emission in human skin cells: A biophotonic comparison between keratinocytes and fibroblasts

Photons participate in many atomic and molecular interactions and processes. Recent biophysical research has discovered an ultraweak radiation in biological tissues. It is now recognized that plants, animal and human cells emit this very weak biophotonic emission which can be readily measured with a sensitive photomultiplier system. UVA laser induced biophotonic emission of cultured cells was used in this report with the intention to detect biophysical changes between young and adult fibroblasts as well as between fibroblasts and keratinocytes. With suspension densities ranging from 1-8x106 cells/ml, it was evident that an increase of the UVA-laser-light induced photon emission intensity could be observed in young as well as adult fibroblastic cells. By the use of this method to determine ultraweak light emission, photons in cell suspensions in low volumes (100 mu l) could be detected, in contrast to previous procedures using quantities up to 10 ml. Moreover, the analysis has been further refined by turning off the photomultiplier system electronically during irradiation leading to the first measurements of induced light emission in the cells after less than 10 mu s instead of more than 100 milliseconds. These significant changes lead to an improvement factor up to 106 in comparison to classical detection procedures. In addition, different skin cells as fibroblasts and keratinocytes stemining from the same donor were measured using this new highly sensitive method in order to find new biophysical insight of light pathways. This is important in view to develop new strategies in biophotonics especially for use in alternative therapies.