Analysis of radicals and radical reaction products in cell signalling and biomolecular damage:the long hard road to gold-standard measures

The field of free radical biology and medicine continues to move at a tremendous pace, with a constant flow of ground-breaking discoveries. The following collection of papers in this issue of Biochemical Society Transactions highlights several key areas of topical interest, including the crucial role of validated measurements of radicals and reactive oxygen species in underpinning nearly all research in the field, the important advances being made as a result of the overlap of free radical research with the reinvigorated field of lipidomics (driven in part by innovations in MS-based analysis), the acceleration of new insights into the role of oxidative protein modifications (particularly to cysteine residues) in modulating cell signalling, and the effects of free radicals on the functions of mitochondria, extracellular matrix and the immune system. In the present article, we provide a brief overview of these research areas, but, throughout this discussion, it must be remembered that it is the availability of reliable analytical methodologies that will be a key factor in facilitating continuing developments in this exciting research area.

A catalytic reactor for the trapping of free radicals from gas phase oxidation reactions

A catalytic reactor for the trapping of free radicals originating from gas phase catalytic reactions is described and discussed. Radical trapping and identification were initially carried out using a known radical generator such as dicumyl peroxide. The trapping of radicals was further demonstrated by investigating genuine radical oxidation processes, e.g., benzaldehyde oxidation over manganese and cobalt salts. The efficiency of the reactor was finally proven by the partial oxidation of cyclohexane over MoO3, Cr2O3, and WO3, which allowed the identification of all the radical intermediates responsible for the formation of the products cyclohexanol and cyclohexanone. Assignment of the trapped radicals was carried out using spin trapping technique and X -band electron paramagnetic resonance spectroscopy. © 2010 American Institute of Physics.

A reliability centered maintenance decision system for a discrete part manufacturing facility

This thesis develops and validates the framework of a specialized maintenance decision support system for a discrete part manufacturing facility. Its construction utilizes a modular approach based on the fundamental philosophy of Reliability Centered Maintenance (RCM). The proposed architecture uniquely integrates System Decomposition, System Evaluation, Failure Analysis, Logic Tree Analysis, and Maintenance Planning modules. It presents an ideal solution to the unique maintenance inadequacies of modern discrete part manufacturing systems. Well established techniques are incorporated as building blocks of the system's modules. These include Failure Mode Effect and Criticality Analysis (FMECA), Logic Tree Analysis (LTA), Theory of Constraints (TOC), and an Expert System (ES). A Maintenance Information System (MIS) performs the system's support functions. Validation was performed by field testing of the system at a Miami based manufacturing facility. Such a maintenance support system potentially reduces downtime losses and contributes to higher product quality output. Ultimately improved profitability is the final outcome. ^

Maltreatment, psychiatric symptoms and human immunodeficiency virus/sexual transmitted infection risk behavior among youth with alcohol and other drug use problems: A person-centered analysis

Multi-problem youth undergoing treatment for substance use problems are at high behavioral risk for exposure to sexually transmitted infections (STIs), including human immunodeficiency virus (HIV). Specific risk factors include childhood adversities such as maltreatment experiences and subsequent forms of psychopathology. The current study used a person-centered analytical approach to examine how childhood maltreatment experiences were related to patterns of psychiatric symptoms and HIV/STI risk behaviors in a sample of adolescents (N = 408) receiving treatment services. Data were collected in face-to-face interviews at two community-based facilities. Descriptive statistics and Latent Profile Analysis (LPA) were used to (a) classify adolescents into groups based on past year psychiatric symptoms, and (b) examine relations between class membership and forms of childhood maltreatment experiences, as well as past year sexual risk behavior (SRB). ^ LPA results indicated significant heterogeneity in psychiatric symptoms among the participants. The three classes generated via the optimal LPA solution included: (a) a low psychiatric symptoms class, (b) a high alcohol symptoms class and (c) a high internalizing symptoms class. Class membership was associated significantly with adolescents’ self-reported scores for childhood sexual abuse and emotional neglect. ANOVAs documented significant differences in mean scores for multiple indices of SRB indices by class membership, demonstrating differential risk for HIV/STI exposure across classes. The two classes characterized by elevated psychiatric symptom profiles and more severe maltreatment histories were at increased behavioral risk for HIV/STI exposure, compared to the low psychiatric symptoms class. The high internalizing symptoms class reported the highest scores for most of the indices of SRB assessed. The heterogeneity of psychiatric symptom patterns documented in the current study has important implications for HIV/STI prevention programs implemented with multi-problem youth. The results highlight complex relations between childhood maltreatment experiences, psychopathology and multiple forms of health risk behavior among adolescents. The results underscore the importance of further integration between substance abuse treatment and HIV/STI risk reduction efforts to improve morbidity and mortality among vulnerable youth. ^

Occupational therapists' attitudes toward family -centered care

The purpose of this study was to examine pediatric occupational therapists attitudes towards family-centered care. Specific attributes identified by the literature (professional characteristics, educational experiences and organizational culture) were investigated to determine their influence on these attitudes. Study participants were 250 pediatric occupational therapists who were randomly selected from the American Occupational Therapy Association special interest sections. ^ Participants received a mail packet with three instruments to complete and mail back within 2 weeks. The instruments were (a) the Professional Attitude Scale, (b) the Professional Characteristics Questionnaire, and (c) the Family-Centered Program Rating Scale. There was a 50% return rate. Data analysis was conducted in SPSS using descriptive statistics, correlations and regression analysis. ^ The analysis showed that pediatric occupational therapists working in various practice settings demonstrate favorable attitudes toward family-centered care as measured by the Professional Attitude Scale. There was no correlation between professional characteristics and educational experiences to therapists' attitudes. A moderate correlation (r = .368, p < .05) was found between the occupational therapists attitudes and the organizational culture of their workplaces. A factor analysis was conducted on the organizational culture instrument (FamPRS) as this sample was exclusively pediatric occupational therapists and the original sample was interdisciplinary professionals. Two factors were extracted using a principal components extraction and varimax rotation, in addition to examination of the scree plot. These two factors accounted for 50% of the total variance of the scores on the instrument. Factor 1, called empowerment accounted for 45.6% of the variance, and Factor 2, responsiveness accounted for 4.3% of the variance of the entire instrument. Stepwise regression analysis demonstrated that these two factors accounted for 16% of the variance toward attitudes clinicians hold toward family-centered care. These factors support the tenets of family-centered care; empowering parents to be leaders in their child's health care and helping organizations become more responsive to family needs. ^ These study findings suggest that organizational culture has some influence on occupational therapists attitudes toward family-centered care (R 2 = .16). These findings suggest educators should consider families as valuable resources when considering program planning in family-centered care at preservice and workplace settings. ^

Subject -centered and problem -based approaches to teaching clinical competence in physical therapy

Physical therapy students must apply the relevant information learned in their academic and clinical experience to problem solve in treating patients. I compared the clinical cognitive competence in patient care of second-year masters students enrolled in two different curricular programs: modified problem-based (M P-B; n = 27) and subject-centered (S-C; n = 41). Main features of S-C learning include lecture and demonstration as the major teaching strategies and no exposure to patients or problem solving learning until the sciences (knowledge) have been taught. Comparatively, main features of M P-B learning include case study in small student groups as the main teaching strategy, early and frequent exposure to patients, and knowledge and problem solving skills learned together for each specific case. Basic and clinical orthopedic knowledge was measured with a written test with open-ended items. Problem solving skills were measured with a written case study patient problem test yielding three subscores: assessment, problem identification, and treatment planning. ^ Results indicated that among the demographic and educational characteristics analyzed, there was a significant difference between groups on ethnicity, bachelor degree type, admission GPA, and current GPA, but there was no significant difference on gender, age, possession of a physical therapy assistant license, and GRE score. In addition, the M P-B group achieved a significantly higher adjusted mean score on the orthopedic knowledge test after controlling for GRE scores. The S-C group achieved a significantly higher adjusted mean total score and treatment management subscore on the case study test after controlling for orthopedic knowledge test scores. These findings did not support their respective research hypotheses. There was no significant difference between groups on the assessment and problem identification subscores of the case study test. The integrated M P-B approach promoted superior retention of basic and clinical science knowledge. The results on problem solving skills were mixed. The S-C approach facilitated superior treatment planning skills, but equivalent patient assessment and problem identification skills by emphasizing all equally and exposing the students to more patients with a wider variety of orthopedic physical therapy needs than in the M P-B approach. ^

The effectiveness of direct -instruction and student -centered teaching methods on students' functional understanding of plagiarism

In an attempt to improve students' functional understanding of plagiarism a variety of approaches were tried within the context of a more comprehensive information literacy program. Sessions were taught as a one hour "module" inside a required communications skills class at a small private university. Approaches taken included control sessions (a straightforward PowerPoint presentation of the material), direct instruction sessions (featuring mostly direct lecture but with some seatwork as well), and student-centered sessions (utilizing role playing and group exercises). Students were taught basic content and definitions regarding plagiarism, what circumstances or instances constitute plagiarism, where to go for help in avoiding plagiarism, and what constitutes appropriate paraphrasing and citation. Pre-test and post-test scores determined students' functional understanding primarily by their ability to recognize properly and improperly paraphrased text, content understanding by their combined total score on a multiple choice quiz, and their attitude and conceptual understanding by their ability to recognize circumstances which would constitute plagiarism. While students improved across all methods the study was unable to identify one that performed significantly better than the others. The results supported the need for more education with regard to plagiarism and suggested a need for perhaps more time on task and/or a mixed approach towards conveying the content.

The effects of student -centered and traditional models of teaching on reading skills

A pre-test, post-test, quasi-experimental design was used to examine the effects of student-centered and traditional models of reading instruction on outcomes of literal comprehension and critical thinking skills. The sample for this study consisted of 101 adult students enrolled in a high-level developmental reading course at a large, urban community college in the Southeastern United States. The experimental group consisted of 48 students, and the control group consisted of 53 students. Students in the experimental group were limited in the time spent reading a course text of basic skills, with instructors using supplemental materials such as poems, news articles, and novels. Discussions, the reading-writing connection, and student choice in material selection were also part of the student-centered curriculum. Students in the control group relied heavily on a course text and vocabulary text for reading material, with great focus placed on basic skills. Activities consisted primarily of multiple-choice questioning and quizzes. The instrument used to collect pre-test data was Descriptive Tests of Language Skills in Reading Comprehension; post-test data were taken from the Florida College Basic Skills Exit Test. A MANCOVA was used as the statistical method to determine if either model of instruction led to significantly higher gains in literal comprehension skills or critical thinking skills. A paired samples t-test was also used to compare pre-test and post-test means. The results of the MANCOVA indicated no significant difference between instructional models on scores of literal comprehension and critical thinking. Neither was there any significant difference in scores between subgroups of age (under 25 and 25 and older) and language background (native English speaker and second-language learner). The results of the t-test indicated, however, that students taught under both instructional models made significant gains in on both literal comprehension and critical thinking skills from pre-test to post-test.

Maltreatment, Psychiatric Symptoms and Human Immunodeficiency Virus/Sexual Transmitted Infection Risk Behavior Among Youth with Alcohol and Other Drug Use Problems: A Person-Centered Analysis

Multi-problem youth undergoing treatment for substance use problems are at high behavioral risk for exposure to sexually transmitted infections (STIs), including human immunodeficiency virus (HIV). Specific risk factors include childhood adversities such as maltreatment experiences and subsequent forms of psychopathology. The current study used a person-centered analytical approach to examine how childhood maltreatment experiences were related to patterns of psychiatric symptoms and HIV/STI risk behaviors in a sample of adolescents (N = 408) receiving treatment services. Data were collected in face-to-face interviews at two community-based facilities. Descriptive statistics and Latent Profile Analysis (LPA) were used to (a) classify adolescents into groups based on past year psychiatric symptoms, and (b) examine relations between class membership and forms of childhood maltreatment experiences, as well as past year sexual risk behavior (SRB). LPA results indicated significant heterogeneity in psychiatric symptoms among the participants. The three classes generated via the optimal LPA solution included: (a) a low psychiatric symptoms class, (b) a high alcohol symptoms class and (c) a high internalizing symptoms class. Class membership was associated significantly with adolescents’ self-reported scores for childhood sexual abuse and emotional neglect. ANOVAs documented significant differences in mean scores for multiple indices of SRB indices by class membership, demonstrating differential risk for HIV/STI exposure across classes. The two classes characterized by elevated psychiatric symptom profiles and more severe maltreatment histories were at increased behavioral risk for HIV/STI exposure, compared to the low psychiatric symptoms class. The high internalizing symptoms class reported the highest scores for most of the indices of SRB assessed. The heterogeneity of psychiatric symptom patterns documented in the current study has important implications for HIV/STI prevention programs implemented with multi-problem youth. The results highlight complex relations between childhood maltreatment experiences, psychopathology and multiple forms of health risk behavior among adolescents. The results underscore the importance of further integration between substance abuse treatment and HIV/STI risk reduction efforts to improve morbidity and mortality among vulnerable youth.

Tecnologia eletroquímica como tratamento alternativo de efluentes derivados da indústria têxtil e petroquímica

In this work, the treatment of wastewater from the textile industry, containing dyes as Yellow Novacron (YN), Red Remazol BR (RRB) and Blue Novacron CD (NB), and also, the treatment of wastewater from petrochemical industry (produced water) were investigated by anodic oxidation (OA) with platinum anodes supported on titanium (Ti/Pt) and boron-doped diamond (DDB). Definitely, one of the main parameters of this kind of treatment is the type of electrocatalytic material used, since the mechanisms and products of some anodic reactions depend on it. The OA of synthetic effluents containing with RRB, NB and YN were investigated in order to find the best conditions for the removal of color and organic content of the dye. According to the experimental results, the process of OA is suitable for decolorization of wastewaters containing these textile dyes due to electrocatalytic properties of DDB and Pt anodes. Removal of the organic load was more efficient at DDB, in all cases; where the dyes were degraded to aliphatic carboxylic acids at the end of the electrolysis. Energy requirements for the removal of color during OA of solutions of RRB, NB and YN depends mainly on the operating conditions, for example, RRB passes of 3.30 kWh m-3 at 20 mA cm-2 for 4.28 kWh m-3 at 60 mA cm-2 (pH = 1); 15.23 kWh m-3 at 20 mA cm-2 to 24.75 kWh m-3 at 60 mA cm-2 (pH 4.5); 10.80 kWh m-3 at 20 mA cm-2 to 31.5 kWh m-3 at 60 mA cm-2 (pH = 8) (estimated data for volume of treated effluent). On the other hand, in the study of OA of produced water effluent generated by petrochemical industry, galvanostatic electrolysis using DDB led to the complete removal of COD (98%), due to large amounts of hydroxyl radicals and peroxodisulphates generated from the oxidation of water and sulfates in solution, respectively. Thus, the rate of COD removal increases with increasing applied current density (15-60 mAcm-2 ). Moreover, at Pt electrode, approximately 50% removal of the organic load was achieved by applying from 15 to 30 mAcm-2 while 80% of COD removal was achieved for 60 mAcm-2 . Thus, the results obtained in the application of this technology were satisfactory depending on the electrocatalytic materials and operating conditions used for removal of organic load (petrochemical and textile effluents) as well as for the removal of color (in the case of textile effluents). Therefore, the applicability of electrochemical treatment can be considered as a new alternative like pretreatment or treatment of effluents derived from textiles and petrochemical industries.

(Table 1, 2) Foraminifera biometric data, and boron isotopic composition of Globigerinoides sacculifer of sediments from the Ontong-Java Plateau

Sediment samples from the Ontong-Java Plateau in the Pacific and the 90° east ridge in the Indian Ocean were used to investigate whether shell size and early diagenesis affect d11B of the symbiont-bearing planktonic foraminifer Globigerinoides sacculifer. In pristine shells from both study locations we found a systematic increase of d11B and Mg/Ca with shell size. Shells in the sieve size class 515-865 µm revealed d11B values +2.1 to +2.3 per mil higher than shells in the 250-380 µm class. This pattern is most likely due to differences in symbiont photosynthetic activity and its integrated effect on the pH of the foraminiferal microenvironment. We therefore suggest smaller individuals must live at approximately 50-100 m water depth where ambient light levels are lower. Using the empirical calibration curve for d11B in G. sacculifer, only shells larger than 425 µm reflect surface seawater pH. Partial dissolution of shells derived from deeper sediment cores was determined by shell weight analyses and investigation of the shell surface microstructure by scanning electron microscopy. The d11B in partially dissolved shells is up to 2 per mil lower relative to pristine shells of the same size class. In agreement with a relatively higher weight loss in smaller shells, samples from the Ontong-Java Plateau show a more pronounced dissolution effect than larger shells. On the basis of the primary size effect and potential postdepositional dissolution effects, we recommend the use of shells that are visually pristine and, in the case of G. sacculifer, larger than 500 ?m for paleoreconstructions.

X-Ray Diffraction Study of Boron Produced by Pyrolysis of Boron Tribromide

The goal of this research was to determine the composition of boron deposits produced by pyrolysis of boron tribromide, and to use the results to (a) determine the experimental conditions (reaction temperature, etc.) necessary to produce alpha-rhombohedral boron and (b) guide the development/refinement of the pyrolysis experiments such that large, high purity crystals of alpha-rhombohedral boron can be produced with consistency. Developing a method for producing large, high purity alpha-rhombohedral boron crystals is of interest because such crystals could potentially be used to achieve an alpha-rhombohedral boron based neutron detector design (a solid-state detector) that could serve as an alternative to existing neutron detector technologies. The supply of neutron detectors in the United States has been hampered for a number of years due to the current shortage of helium-3 (a gas used in many existing neutron detector technologies); the development of alternative neutron detector technology such as an alpha-rhombohedral boron based detector would help provide a more sustainable supply of neutron detectors in this country. In addition, the prospect/concept of an alpha-rhombohedral boron based neutron detector is attractive because it offers the possibility of achieving a design that is smaller, longer life, less power consuming, and potentially more sensitive than existing neutron detectors. The main difficulty associated with creating an alpha-rhombohedral boron based neutron detector is that producing large, high purity crystals of alpha-rhombohedral boron is extremely challenging. Past researchers have successfully made alpha-rhombohedral boron via a number of methods, but no one has developed a method for consistently producing large, high purity crystals. Alpha-rhombohedral boron is difficult to make because it is only stable at temperatures below around 1100-1200 °C, its formation is very sensitive to impurities, and the conditions necessary for its formation are not fully understood or agreed upon in the literature. In this research, the method of pyrolysis of boron tribromide (hydrogen reduction of boron tribromide) was used to deposit boron on a tantalum filament. The goal was to refine this method, or potentially use it in combination with a second method (amorphous boron crystallization), to the point where it is possible to grow large, high purity alpha-rhombohedral boron crystals with consistency. A pyrolysis apparatus was designed and built, and a number of trials were run to determine the conditions (reaction temperature, etc.) necessary for alpha-rhombohedral boron production. This work was focused on the x-ray diffraction analysis of the boron deposits; x-ray diffraction was performed on a number of samples to determine the types of boron (and other compounds) formed in each trial and to guide the choices of test conditions for subsequent trials. It was found that at low reaction temperatures (in the range of around 830-950 °C), amorphous boron was the primary form of boron produced. Reaction temperatures in the range of around 950-1000 °C yielded various combinations of crystalline boron and amorphous boron. In the first trial performed at a temperature of 950 °C, a mix of amorphous boron and alpha-rhombohedral boron was formed. Using a scanning electron microscope, it was possible to see small alpha-rhombohedral boron crystals (on the order of ~1 micron in size) embedded in the surface of the deposit. In subsequent trials carried out at reaction temperatures in the range of 950 °C – 1000 °C, it was found that various combinations of alpha-rhombohedral boron, beta-rhombohedral boron, and amorphous boron were produced; the results tended to be unpredictable (alpha-rhombohedral boron was not produced in every trial), and the factors leading to success/failure were difficult to pinpoint. These results illustrate how sensitive of a process producing alpha-rhombohedral boron can be, and indicate that further improvements to the test apparatus and test conditions (for example, higher purity/cleanliness) may be necessary to optimize the boron deposition. Although alpha-rhombohedral boron crystals of large size were not achieved, this research was successful in (a) developing a pyrolysis apparatus and test procedure that can serve as a platform for future testing, (b) determining reaction temperatures at which alpha-rhombohedral boron can form, and (c) developing a consistent process for analyzing the boron deposits and determining their composition. Further experimentation is necessary to achieve a pyrolysis apparatus and test procedure that can yield large alpha-rhombohedral boron crystals with consistency.

Preparation of Boron by Pyrolytic Decomposition of Boron Tribromide

The national shortage of helium-3 has made it critical to develop an alternative to helium-3 neutron detectors. Boron-10, if it could be produced in macroscopic alpha-rhombohedral crystalline form, would be a viable alternative to helium-3. This work has determined the critical parameters needed for the preparation of alpha-rhombohedral boron by the pyrolytic decomposition of boron tribromide on tantalum wire. The primary parameters that must be met are wire temperature and feedstock purity. The minimum purity level for boron tribromide was determined to be 99.999% and it has been found that alpha-rhombohedral boron cannot be produced using 99.99% boron tribromide. The decomposition temperature was experimentally tested between 830°C and 1000°C. Alpha-rhombohedral boron was found at temperatures between 950°C and 1000°C using 99.999% pure boron tribromide.