bluuebunny/crossref_metadata_2025 huggingface dataset:
Leadership Development for Organizational Change in a New U.K. University
Authors: Turnbull Sharon , Edwards Gareth
Published: July 2005

The problem and the solution. This article reports on the findings of a case study of an organizational development intervention within a new university in the United Kingdom. Previous research into the leadership of higher education has highlighted a number of apparently inevitable tensions. The findings of the case study uncovered a number of complex and interrelated tensions. The article concludes by discussing the implications of these tensions for organization development and human resource practitioners, theorists, and consultants.
What Would Be Different if Higher Educational Institutions Were Learning Organizations?
Authors: Watkins Karen E.
Published: July 2005

The problem and the solution.What would be different if we structured our colleges and departments in higher education to be learning organizations? Using the dimensions of a learning organization, principles, policies, and practices can be created to promote ongoing change and development in higher education.
Organization Development and Change in Universities: Implications for Research and Practice
Authors: Torraco Richard J. , Hoover Richard E.
Published: July 2005

The problem and the solution. This article will summarize what is known about the use of organization development (OD) in universities based on the foregoing cases. The following questions will be addressed: What lessons have been learned about OD in universities? Why have some change strategies been successful in developing organizational capabilities, particularly the ability of university personnel to identify and solve their own work-related problems? What does the examination of these cases contribute to the tools and methods available to OD professionals and consultants?
Community Involvement in the Conduct of a Health Education Intervention and Research Project: Community Action Against Asthma
Authors: Edgren Katherine K. , Parker Edith A. , Israel Barbara A. , Lewis Toby C. , Salinas Maria A. , Robins Thomas G. , Hill Yolanda R.
Published: July 2005

There is a need for more guidance on how to implement community-based participatory research, particularly on the roles of community members, throughout the process. This article focuses on how a Steering Committee, composed of representatives from community-based organizations, a local health department, an integrated health care system, and academia from the University of Michigan, participated in the design and implementation of a children’s asthma study in Detroit, Michigan: Community Action Against Asthma. In addition, this article focuses on the role of community members as data collectors, examining a variety of sophisticated data collection roles. A description and analysis of how community members shaped and participated in the project, the lessons learned, and recommendations for practitioners are also presented.
Planning and the Professional Preparation of Health Educators: Implications for Teaching, Research, and Practice
Authors: Linnan Laura A. , Sterba Katherine Regan , Lee Ann Marie , Bontempi Jean Breny , Yang Jingzhen , Crump Carolyn
Published: July 2005

Planning skills are one of the seven essential responsibilities of health educators, according to the National Commission of Health Education Credentialing program; yet little information is available about who provides training in planning, what type of training is offered, and what planning models are taught. A survey of 253 accredited graduate and undergraduate health education programs (response rate = 56%) was undertaken to gather information about planning and the professional preparation of health educators. Results revealed that planning instructors were primarily full-time, experienced, and about one half were CHES certified. Overall, 88% (113/129) of respondents taught the PRECEDE-PROCEED model, and 62% (81/131) taught the planned approach to community health (PATCH) model. Few planning differences were found at the graduate and undergraduate levels. Content analysis of 56 course syllabi revealed that 80% (45/56) required students to complete a program plan proposal or document as the culminating project for the course. Implications for teaching, research, and practice are discussed.
Taking the Transtheoretical Model Into the Field: A Curriculum for Lay Health Advisors
Authors: Kobetz Erin , Vatalaro Katherine , Moore Alexis , Earp Jo Anne
Published: July 2005

The transtheoretical model (TTM) is a commonly applied theoretical perspective for understanding mammography behaviors and improving the effectiveness of one-on-one counseling. The North Carolina Breast Cancer Screening Program (NC-BCSP) developed a training curriculum to incorporate TTM into the advising practices of lay health advisors (LHAs). The TTM helped “natural helper” LHAs understand that women in their rural North Carolina communities were likely to be in different stages for mammography screening and hence required different messages. NC-BCSP staff believed that by combining an understanding of TTM with LHAs’ natural helping abilities we potentially increased the effectiveness of LHA advising. Our limited evaluation, based on LHA feedback, suggests the curriculum is a useful training tool, even for those unfamiliar with behavior change models. Our TTM curriculum serves as an example of a health behavior theory successfully operationalized outside academia for use in the field by lay people.
Using Intervention Mapping to Adapt an Effective HIV, Sexually Transmitted Disease, and Pregnancy Prevention Program for High-Risk Minority Youth
Authors: Tortolero Susan R. , Markham Christine M. , Parcel Guy S. , Peters Ronald J. , Escobar-Chaves S. Liliana , Basen-Engquist Karen , Lewis Holly L.
Published: July 2005

Although many programs have been developed to reduce adolescent pregnancy and sexually transmitted diseases (STDs) (including HIV), with some showing promise in reducing sexual risk-taking behavior, little guidance has been given as to how to adapt existing interventions to new communities. When adapting a program, effective elements deemed necessary to change behaviors need to be preserved, while cultural competence and relevance for the new population must be considered in creating new elements. To address these needs, the authors describe the application of a systematic process, intervention mapping (IM), to adapt a theory-based, multicomponent HIV, STD, and pregnancy prevention program titled Safer Choices to a new target population, at-risk youth attending alternative schools and at risk of dropping out. IM is a detailed process that provides planners with a systematic method for decision making in each phase of developing or adapting an intervention to influence changes in behavior and environmental conditions.
Community Development Model for Public Health Applications: Overview of a Model to Eliminate Population Disparities
Authors: Robinson Robert G.
Published: July 2005

For well over two decades, the public health community has undertaken a broad range of initiatives to identify and eliminate various health-related disparities among populations. The Centers for Disease Control and Prevention’s (CDC) Office on Smoking and Health (OSH), for example, has committed resources to help states eliminate population disparities related to tobacco use. These initiatives have enjoyed a degree of success and some measurable decreases in population disparities. However, traditional public health approaches that are overly influenced by reductionist paradigms more content with risk factor assessment of at-risk strata may not be sufficient to produce successful results when applied to more intractable disparities. The elimination of disparities will require a more encompassing and comprehensive approach that addresses both population strata at risk and the communities in which they reside. This article proposes a new, concentrated model to address the elimination of population disparities—a model that focuses on community as the critical unit of analysis and action to achieve success.
National Survey of Cancer Educators: Salary and Budget
Authors: Deshler Amy M.B. , Cheney Lydia C. , Villejo Louise A.
Published: July 2005

The National Cancer Institute’s Cancer Patient Education Network (CPEN) is composed of cancer education leaders from National Cancer Institute (NCI)-designated comprehensive and clinical cancer centers throughout the United States. Despite this commonality, the role and responsibilities of CPEN members vary across institutions. In an effort to further understand the common-alties and variances among the membership, the authors undertook a research project addressing salary and budget issues across NCI-designated cancer centers. The purpose of this study was to benchmark salaries and budgets of cancer educators at NCI-designated cancer centers; provide information to support a competitive salary range based on benchmarking with peers responsible for cancer patient education; and glean information on CPEN membership, roles, education levels, and job functions. This article highlights lessons learned and offers suggestions for using this information in a broader capacity for other cancer patient educators and patient educators in general.
Media Advocacy and Underage Drinking Policies: A Study of Louisiana News Media From 1994 Through 2003
Authors: Harwood Eileen M. , Witson Jean C. , Fan David P. , Wagenaar Alexander C.
Published: July 2005

The communications literature firmly establishes the significant role of media advocacy in setting public agenda and influencing the direction of public opinion on social issues. Recent public health campaigns embrace media advocacy as an integral part of efforts to change public health policies, yet further studies are needed on the best strategies to promote legislative action. This article examines press coverage in the Baton Rouge Advocate and the New Orleans Times-Picayune newspapers and Louisiana State legislation pertaining to underage drinking from January 1994 to June 2003 and focuses on evidence of media priming and framing of underage drinking and four related legislative policies. High press coverage of alcohol bills during the legislative process was associated with defeated legislation, whereas little or no press coverage was associated with bills successfully passed into law. The authors conclude that more work is needed to understand how media advocacy strategies may hinder enactment of bills.
Clinical factors predictive of outcome with bortezomib in patients with relapsed, refractory multiple myeloma
Authors: Richardson Paul Gerard Guy , Barlogie Bart , Berenson James , Singhal Seema , Jagannath Sundar , Irwin David , Rajkumar S. Vincent , Hideshima Teru , Xiao Hugh , Esseltine Dixie , Schenkein David , Anderson Kenneth C. ,   for the SUMMIT Investigators
Published: July 2005

Bortezomib, a potent and reversible proteasome inhibitor, affects the myeloma cell and its microenvironment, resulting in down-regulation of growth and survival signaling pathways and durable responses in patients with relapsed and refractory myeloma. Potential associations between baseline parameters and outcomes with bortezomib were explored in 202 patients who received bortezomib 1.3 mg/m2 twice weekly for 2 weeks every 3 weeks for up to 8 cycles in a phase 2 trial. Using European Group for Blood and Marrow Transplantation criteria, the response rate (complete or partial response) to bortezomib alone was 27% and was not associated with sex, race, performance status, isotype, chromosome 13 deletion, number or type of previous therapies, or concentration of hemoglobin or β2-microglobulin. By multivariate analysis, factors associated with lower response were being age 65 or older versus younger than 65 (19% vs 32%; P < .05) and plasma-cell infiltration in bone marrow greater than 50% versus 50% or less (20% vs 35%; P < .05). Factors that may be indicative of tumor burden (bone marrow plasma-cell infiltration greater than 50%, hypoalbuminemia, thrombocytopenia) were predictive of overall survival. Chromosome 13 deletion and elevated β2-microglobulin, generally considered poor prognostic factors, were not predictive of poor outcome with bortezomib in this study.
Quantitative analysis of EGR proteins binding to DNA: assessing additivity in both the binding site and the protein
Authors: Liu Jiajian , Stormo Gary D
Published: July 2005

Background

Recognition codes for protein-DNA interactions typically assume that the interacting positions contribute additively to the binding energy. While this is known to not be precisely true, an additive model over the DNA positions can be a good approximation, at least for some proteins. Much less information is available about whether the protein positions contribute additively to the interaction.

Results

Using EGR zinc finger proteins, we measure the binding affinity of six different variants of the protein to each of six different variants of the consensus binding site. Both the protein and binding site variants include single and double mutations that allow us to assess how well additive models can account for the data. For each protein and DNA alone we find that additive models are good approximations, but over the combined set of data there are context effects that limit their accuracy. However, a small modification to the purely additive model, with only three additional parameters, improves the fit significantly.

Conclusion

The additive model holds very well for every DNA site and every protein included in this study, but clear context dependence in the interactions was detected. A simple modification to the independent model provides a better fit to the complete data.
Systematic review of hypnotherapy for treating symptoms in terminally ill adult cancer patients
Authors: Rajasekaran M , Edmonds P M , Higginson I L
Published: July 2005

The aim of this review was to find the evidence for or against the use of hypnotherapy in the treatment of symptoms in terminally ill adult cancer patients. The title and abstract were evaluated following a search through Index Medicus/MEDLINE, EMBASE, CINHAHL, CancerLit, AHMED, Psychinfo, CISCOM, Cochrane and DARE. Search terms included hypnotherapy, cancer, terminal care and palliative care. Inclusion criteria included systematic reviews, randomized controlled trials, observational and prospective studies, retrospective surveys, case studies and reports. A total of 27 papers were evaluated. Two reviewers assessed the studies, one extracted the relevant data and 10% were evaluated independently by a third reviewer. The 27 papers comprised a randomized controlled trial, an observational study, a retrospective questionnaire and 24 case studies. Hypnotherapy was used to treat a variety of symptoms, including pain, anxiety and depression. The poor quality of the studies and heterogeneity of the study population limited further evaluation; further research is required to understand the role of hypnotherapy in managing symptoms.
The Norwegian Doloplus-2, a tool for behavioural pain assessment: translation and pilot-validation in nursing home patients with cognitive impairment
Authors: Hølen Jacob C , Saltvedt Ingvild , Fayers Peter M , Bjørnnes Marit , Stenseth Guri , Hval Bjørn , Filbet Marilène , Loge Jon Håvard , Kaasa Stein
Published: July 2005

Background: Pain assessment is challenging in cognitively impaired (CI) patients due to inadequate self-report skills and observational ratings are an alternative. The Doloplus-2 is developed for pain assessment in the CI and rates somatic, psychomotor and psychosocial behaviours as indicators of pain. Aims: To translate the Doloplus-2 into Norwegian, to test the Doloplus-2 with regard to criterion validity and to obtain the administrators' evaluation of the clinical performance of the Doloplus-2. Methods: Nurses at three nursing homes, in collaboration with two research assistants, administered the Doloplus-2 to 59 patients with dementia. The results were compared against experienced clinicians' pain ratings. Regression analyses were performed to explore each different item's contribution to the total pain score. The administrators also completed a debriefing questionnaire. Results: The instrument was translated according to international guidelines. Regression analyses demonstrate that the Doloplus-2 score accounts for 62% (R2) of the expert score and that the four most informative items could explain 68% of the expert score. Analyses of the different Doloplus-2 items indicate that facial expressions explain most and social life least of the expert's pain ratings. The administrators reported that Doloplus-2 was helpful and easy to administer, but questioned the validity of the psychosocial domain. Conclusions: The Norwegian Doloplus-2 demonstrates satisfactory criterion validity and clinical value in this pilot study. However, the content of the instrument needs a general re-evaluation, especially with regard to the psychosocial items.
Carotid stenting for impending carotid blowout: suitable supportive care for head and neck cancer patients?
Authors: Desuter G , Hammer F , Gardiner Q , Grégoire V , Machiels J P , Hamoir M , Goffette P
Published: July 2005

Background: Carotid blowout (CB) represents a dramatic end-of-life situation for palliative head and neck cancer patients, their relatives and caregivers. Recently, endovascular therapy has been proposed for head and neck surgical patients. Preliminary reports showed a better outcome with less morbidity compared to the previous treatment modalities. However, the specific use of such techniques for palliative head and neck cancer patients has not been previously described. Method: Retrospective review of two cases of head and neck cancer patients receiving palliative care, presenting with a CB, managed with endovascular stent placement. Results: Bleeding was effectively stopped by the procedure in both cases. Both patients developed a post-procedure thromboembolism, which was immediately treated by appropriate anticoagulation therapy. Neurological symptoms resolved within 24 hours allowing rapid hospital discharge. One patient died at home seven months later. The second patient is alive five months after the procedure. No recurrence of CB occurred in either patient. Conclusions: Endovascular stent placement for CB allows a rapid arrest of bleeding and permits the use of anticoagulation therapy in order to avoid long-term neurological injury. In our view, carotid stenting should be considered as valid supportive care for palliative head and neck patients presenting with a CB.
Older adults' attitudes to death, palliative treatment and hospice care
Authors: Catt Susan , Blanchard Martin , Addington-Hall Julia , Zis Maria , Blizard Robert , King Michael
Published: July 2005

Background: Cancer patients who receive care from specialist palliative care services in the UK are younger than those who do not receive this care. This may be explained by agerelated differences in attitudes to end-of-life care. Objective: To determine the relationship between age and i) attitudes to death and preparation for death; and ii) knowledge about, and attitudes to, cancer and palliative care. Design: Interviews with older people, using a novel questionnaire developed using nominal groups. Main comparisons were made between people aged 55-74 with those aged 75 years and over. Setting: General practices in London. Subjects: 129 people aged 55-74 and 127 people aged 75 years or over on the lists of general practitioners. Methods: A cross-sectional survey to determine knowledge and experience of hospice care; preparation for end-of-life; and attitudes to end-of-life issues. Results: Participants were knowledgeable about specialist palliative care and almost half had some indirect contact with a hospice. People aged <74 were less likely than younger participants to want their doctor to end their life in a terminal illness. Although they believed death was easier to face for older people, they did not believe that younger people deserved more consideration than older people when dying, or that they should have priority for hospice care. Education, social class, hospice knowledge and anxiety about death had little influence on overall attitudes. Conclusions: The relative under-utilization of hospice and specialist palliative care services by older people with cancer in the UK cannot be explained by their attitudes to end-of-life issues and palliative care.
Renal dialysis abatement: lessons from a social study
Authors: Ashby Michael , Hoog Corinne op’t , Kellehear Allan , Kerr Peter G , Brooks Denise , Nicholls Kathy , Forrest Marian
Published: July 2005

Aim: This study aimed to examine the reasons why some people chose to abate (i.e., stop or not start) renal dialysis, together with the personal and social impact of this decision on the person concerned, and/or their families. Method: A qualitative design based on the principles of Grounded Theory was employed. Semi-structured interviews were conducted with sixteen patients and/or carers (depending on whether the patient was able to be interviewed) where the issue of dialysis abatement was being considered, or had recently been decided. Results: Of 52 participants considered for entry into the study 41 were ineligible, with impaired cognition, rapid medical deterioration, and inability to speak sufficient English being the main reasons for exclusion. The desire not to burden others and the personal experience of a deteriorating quality of life were crucial elements in the decision to stop or decline dialysis. The problem of prognostic uncertainty and a sense of abandonment were also prominently expressed. Conclusions: From this small Australian sample, it appears that there would be considerable potential benefit from a more proactive and open approach to end-of-life issues, with incorporation of the clinical and health promoting principles of palliative care into renal dialysis practice. The high number of exclusions shows how sick and unstable this population of patients is, but the issue of data gathering from people whose main language is not English requires attention.
The Cognitive Structure of Social Categories*
Authors: Dahlgren Kathleen
Published: July 2005

Support for the prototype theory of categorization was found in a study of the structure of social categories. Though occupational terms such as DOCTOR are socially defined, they do not have the classical structure their clear definitional origins would predict. Conceptions of social categories are richer and more complex than those of physical object categories and subjects agree upon them. Comparison of various instructions for eliciting attributes of categories showed that whether subjects are asked to define a term, give characteristics, or describe ways they recognize members of categories, the attributes they list contribute to a prototype structure. These data provide evidence against the view that prototype structure is relevant only to an identification procedure and not to the core of concepts, as has been suggested.
Performance enhancement in transonic axial compressors using blade tip injection coupled with casing treatment
Authors: Beheshti B. H. , Farhanieh B , Ghorbanian K , Teixeira J. A. , Ivey P. C.
Published: July 2005

The casing treatment and flow injection upstream of the rotor tip are two effective approaches in suppressing instabilities or recovering from a fully developed stall. This paper presents numerical simulations for a high-speed transonic compressor rotor, NASA Rotor 37, applying a state-of-the-art design for the blade tip injection. This is characterized by introducing a jet flow directly into the casing treatment machined into the shroud. The casing treatment is positioned over the blade tip region and exceeds the impeller axially by ∼30 per cent of the tip chord both in the upstream and in the downstream directions. To numerically solve the governing equations, the three-dimensional finite element based finite volume method CFD solver CFX-TASCflow (version 2.12.1) is employed. For a compressible flow with varying density, Reynolds-averaging leads to appearance of complicated correlations. To avoid this, the mass-weighted or Favre-averaging is applied. Using an injected mass flow of 2.4 per cent of the annulus flow, the present design can improve stall margin by up to 7 per cent when compared with a smooth casing compressor without tip injection. This research can lead to an optimum design of recirculating casing treatments or other mechanisms for performance enhancement applying tip flow injection.
A scaling study of a combined microcombustor and heat engine system
Authors: Peterson R. B.
Published: July 2005

A general heat engine model is developed for determining the scaling characteristics of small combustion-driven energy systems. The model is composed of a Carnot heat engine and a combustor operating at a specified temperature dictated by the thermodynamic maximum power point. Considerations have been made for thermal conduction losses to the surroundings and heat recovery from the exhaust stream of the combustor. Modelling of the conduction heat loss is necessary due to the increased importance of this effect upon a reduction in size. This model is used to determine the ideal system efficiency as a function of characteristic length. This length is then varied from mesoscale dimensions to the microscale with the overall system efficiency being determined at each point. The scaling study provides a sense for the ultimate size limitations imposed on combustion-driven engines due to thermal loss mechanisms to the surroundings. Although a high degree of idealization is employed, this analysis shows that submillimetre engine/combustor systems appear impractical, but characteristic sizes in the range of a few millimetres are feasible, at least in regards to the thermal loss mechanisms. This study also shows that systems having a conduction parameter greater than approximately 0.5 do not benefit significantly from heat exchanger NTU values greater than 3 due to the diminishing benefits of heat recovery with larger conduction losses.
An intelligent monitoring system for the detection of slag deposition on a pulverized coal fired burner
Authors: Tan C. K. , Wilcox S. J. , Ward J , Lewitt M
Published: July 2005

The objective of this paper is to describe the further development of a monitoring system to detect the presence of so-called burner eyebrows, i.e. relatively large deposits of slag around the burner quarl in pulverized coal fired boilers. Experiments were undertaken with a range of coals and with various artificial eyebrows constructed from cast refractory inserts. The system uses a microphone to detect combustion noise and an infrared sensor which measures flame radiation, and the signals from these cheap, easily installed sensors were analyzed by a hybrid neural network. In tests with two coals, the system was able to distinguish the different eyebrows with a high degree of accuracy if representative data were used to train the network for each particular coal. In further tests with a range of six different coals, the system was able to distinguish between a clean burner and one fitted with a particular sized eyebrow. In this case, it proved to be possible to use only the features from three of the coals in the training process and the data from the remaining fuels for validation. The monitoring system, therefore, appears to be relatively independent of changes to the coal fired by the burner if trained with a representative range of coals. Finally, this paper presents a possible method to detect burner eyebrows via the evaluation of so-called ‘eyebrow indices’ using a self-organizing map which is trained solely using clean burner sensor patterns.
Power generation system using two models for an inertial confinement fusion reactor
Authors: Kien L. C. , Harada N
Published: July 2005

In this study, the series cooling model and the parallel cooling model of inertial confinement fusion reactor were used as a heat source for driving the MHD/Gas Turbine combined power generation system. This reactor is designed with the first wall and the blanket, which are used to collect the products of fusion reactions (including X-ray, charged particles, and neutrons) and to convert the fusion energy into thermal energy. In the series cooling model, the coolant after being heated in the blanket is re-heated again in the first wall, therefore, > 2000 K working gas can be obtained. In the parallel cooling model, 1300-1700 K working gas was extracted from the blanket for driving the Gas Turbine cycle and high temperature 2000-2400 K working gas can be extracted from the first wall for driving the MHD cycle. The system using the series cooling model reached a highest plant efficiency of 58.34 per cent whereas the system using the parallel cooling model reached a highest plant efficiency of 57.49 per cent. It was found that the enthalpy extraction and the first wall output temperature both affected the fusion output power, therefore, the plant efficiency was greatly affected by these factors. With the increase of reactor output temperature, the plant efficiency increased, however, because of the temperature limitation of the Gas Turbine and blanket, an output temperature > 2400 K from reactor cannot be used.
Self-assembled coordination cage as a molecular flask
Authors: Yoshizawa Michito , Fujita Makoto
Published: July 2005

Cavity-directed chemical transformations represent one of the most important features in 3-D host chemistry, yet they are unexplored as synthetic receptors. We are developing such functions with the large cavity of self-assembled cages, particularly an M6L4-type cage. The photodimerization of olefins within this cage shows remarkable rate enhancement, perfect regio- and stereoselection, and high pairwise selection (when two different olefins are used) giving only the cross [2+2] adduct. Another intriguing property of the cavity is the stabilization of labile molecules by encapsulation. We succeeded in trapping labile molecules by in situ preparation from small components coming through small portals of the cage. For example, hydrolysis and condensation of PhSi(OMe)3, which ordinarily provides a sophisticated Si-O 3-D network (so-called sol-gel condensation), selectively gave a cyclic trimer, [PhSi(OH)O]3, in a "ship-in-a-bottle" fashion. Cavity-sensitized photochemical oxidation of alkanes within the cage is also discussed.
Development of methods suitable for natural product synthesis: The azadirachtin story
Authors: Ley Steven V.
Published: July 2005

Our synthesis work on the insect antifeedant azadirachtin is described. Particular emphasis is placed on the key coupling of a left-hand decalin fragment with a right-hand hydroxydihydrofuran acetal unit via a Claisen rearrangement reaction of an intermediate propargylic enol ether. New chemistry has been developed leading to control of an endo-selective intramolecular Diels–Alder reaction using silicon, which was essential for the construction of the appropriately functionalized decalin fragment. In order to install the five-ring hemiacetal of azadirachtin, we also developed a new ring contraction protocol via an intermediate six-ring cyano ester.
Synthesis of leucascandrolide A
Authors: Wang Ying , Janjic Jelena , Kozmin Sergey A.
Published: July 2005

This paper describes a convergent and stereocontrolled synthesis of leucascandrolide A, a marine natural product that exhibits potent growth inhibition of mammalian and yeast cells. The approach features a substrate-directed relay of the stereochemical information via a series of highly diastereoselective transformations. Spontaneous macrolactolization discovered during this synthetic exercise has provided an unprecedented access to this marine macrolide and demonstrates a new tactic for assembling large-ring systems based on the thermodynamic preference of hemiacetalization.
Multicomponent reactions based on nucleophilic carbenes and their applications in organic synthesis
Authors: Nair Vijay , Menon Rajeev S. , Sreekumar V.
Published: July 2005

Zwitterionic intermediates generated from the addition of nonprotic nucleophiles to activated acetylenes are intercepted with various third components constituting novel multicomponent organic transformations. Catalytic amounts of an organic base like pyridine were found to trigger reactions between an electrophilic acetylene and a variety of electrophiles. The reactions proceed through dipolar intermediates and show high stereoselectivity.
Annulation of propargylic dithioacetals leading to furan-containing oligoaryls
Authors: Luh Tien-Yau
Published: July 2005

Reaction of propargylic dithioacetals with BuLi followed by treatment with dialdehydes yields the corresponding allenyl carbinols which can be cyclized to give the 2,3,5-trisubstituted furans. The use of this strategy for the synthesis of a range of alternating benzene-furan oligoaryls is described.
New catalytic methods for the synthesis of selectively substituted aromatics through palladacycles
Authors: Catellani Marta , Motti Elena , Faccini Fiorenza , Ferraccioli Raffaella
Published: July 2005

Joint palladium and norbornene catalysis for selective aromatic functionalization via palladacycles is reported. Both alkylation and arylation of aromatics are considered after a brief outlook on the mechanism. These are multistep reactions that proceed in ordered sequences and are chemio-, regio-, and stereoselective. The study of the single steps with isolation of the organometallic species involved has allowed us to detect subtle steric and electronic effects which have been exploited to achieve catalytic reactions. Recent developments of aromatic alkylation and arylation are reported, in particular, condensed heterocyclic ring formation involving dialkylated arylpalladium complexes or both symmetrically and unsymmetrically substituted biphenylylpalladium complexes.
Combinatorial approach to the discovery of chiral catalysts for asymmetric reactions
Authors: Ding Kuiling
Published: July 2005

The powerfulness of a combinatorial approach in the discovery of novel chiral catalyst systems, particularly for the development of highly efficient, enantioselective, and practical catalysts for asymmetric reactions, was demonstrated by screening modular chiral catalyst libraries created by the strategy of two-component ligand modification of metal ions on the basis of molecular recognition and assembly.
Asymmetric catalytic addition of diorganozinc reagents to imines: Scope and application
Authors: Charette André B. , Boezio Alessandro A. , Côté Alexandre , Moreau Elaine , Pytkowicz Julien , Desrosiers Jean-Nicolas , Legault Claude
Published: July 2005

The copper-catalyzed diorganozinc addition to N-diphenylphosphinoylimines was shown to proceed with a very high degree of enantiocontrol if the reaction was run in the presence of Me-DuPHOS monoxide ligand (BozPHOS). The scope of the reaction is described as well as our efforts to identify the nature of the enantioactive metal complex responsible for the high asymmetric induction.
Enantioselective iodocyclization and mercuriocyclization of γ-hydroxy-cis-alkenes
Authors: Kang Sung Ho , Kang Suk Youn , Park Chul Min , Kwon Hyo Young , Kim Mihyong
Published: July 2005

Asymmetric iodocyclization and mercuriocyclization of γ-hydroxy-cis-alkenes have been established. The iodocyclization has been attained with 1.2 equiv of iodine in the presence of the catalyst system prepared from 0.3 equiv of (R,R)-salen−Co(II) complex and 0.75 equiv of NCS to produce 2-substituted tetrahydrofurans with up to 90% ee. The mercuriocyclization has been achieved using 1.2 equiv of Hg(II) complexed with 4-(2-naphthyl)bisoxazoline (1:1 complex) in the presence of 5 equiv of K2CO3 and 10 equiv of MeOH to procure 2-substituted tetrahydrofurans with up to 95 % ee.
Biomimetic and organocatalytic approaches to oxidation catalysis
Authors: Berkessel Albrecht
Published: July 2005

The lecture summarized our recent work in the fields of (i) catalytic asymmetric epoxidation and cyclopropanation, (ii) C–C coupling reactions, and (iii) dynamic kinetic resolution (DKR). The first section describes the use of chiral Ru-porphyrins as catalysts for the asymmetric epoxidation and cyclopropanation of nonfunctionalized olefins, and of peptides and alkaloid-based phase-transfer catalysts for the asymmetric epoxidation of enones. The second section highlights the application of the DIANANE-salen ligands (DIANANE: endo,endo-2,5-diamino-norbornane) to the asymmetric Nozaki–Hiyama–Kishi coupling of aldehydes with allylic and vinylic electrophiles, and of N-tosyl proline amides for asymmetric aldol additions. In the final section, bifunctional urea-based organocatalysts for the DKR of azlactones to provide enantiomerically enriched amino acid esters are presented.
Factors Affecting Quantitative Studies of Surface Adsorbates Using Multiresonant Second-Order Nonlinear Spectroscopy
Authors: Cresswell Stephanie A. , Steehler Jack K.
Published: July 2005

Fundamental quantitative studies of dyes (Nile Blue 690, Oxazine 725, Cresyl Violet 670) adsorbed to fused-silica surfaces were performed to determine the usefulness of multiresonant χ(2) spectroscopy as a surface-selective tool. Factors considered include laser-induced desorption, saturation of resonant transitions, choice of the most useful molecular resonances, molecular orientation, laser incidence angle, and laser polarization. In the most restrictive case (doubly resonant), elimination of desorption and saturation problems required laser power densities below 67 kW/cm2, while for a nonresonant case power densities of 2 GW/cm2 could be used. The resonant enhancement of χ(2) and limitations on usable power densities combine to yield similar detection limits for resonant and nonresonant studies. Detection limits of 0.037 to 0.17 monolayer were obtained for various multiresonant and nonresonant cases. The multiresonant case retains the important advantage of selecting a single mixture component for examination, as demonstrated by an initial study of an adsorbate mixture system.
Dynamic Range Enhancement of Photodiode Array Spectra
Authors: Wirsz Douglas F. , Browne R. J. , Blades M. W.
Published: July 2005

The dynamic range of the photodiode array is typically 30 dB. In situations requiring a dynamic range greater than 30 dB, the photomultiplier tube is a popular alternative, but the advantage of multiwavelength simultaneous data acquisition—possible with a photodioide array—is lost. A method has been developed to enhance the dynamic range of spectra taken with the use of a photodiode array. A set of spectra is collected under computer control at varied integration times, and the optimum integration time is chosen individually for each detecting element. As a result, an improvement in the suppression of the noise floor is achieved, leading to a single spectrum with an enhanced dynamic range of 50 dB.
Phase-Modulation Fluorometry for On-Line Liquid Chromatographic Detection and Analysis of Mixtures of Benzo(k)fluoranthene and Benzo(b)fluoranthene
Authors: Cobb W. Tyler , McGown Linda B.
Published: July 2005

A phase-modulation fluorometer was used for on-line detection of benzo(k)fluoranthene and benzo(b)fluoranthene in a mixture of the two that was isocratically eluted from a high-performance liquid chromatographic column. Three different mobile-phase solvent compositions provided three degrees of chromatographic separation, ranging from complete to almost no separation. Fluorescence lifetimes were calculated from phase and modulation data that were collected at three different excitation modulation frequencies. Heterogeneity analysis was then used to calculate the fluorescence lifetimes and fractional intensity contributions of each component at each point along the chromatograms. The fractional intensity contributions were multiplied by the fluorescence intensities in the steady-state chromatogram of the mixture in order to construct the fluorescence intensity chromatograms of the individual components. Retention times and fluorescence lifetimes of the components obtained from the constructed chromatograms were in good agreement with values obtained from steady-state chromatograms of the individual components. Relative errors of the peak intensities were as high as 23%. Batch experiments were also performed to determine the best results that could be expected for the heterogeneity analysis of mixtures of the two components in the solvent systems that were used in the chromatographic experiments.
Detection and Determination of Minor Components in Nominally Pure Solids by Raman Spectroscopy
Authors: Mann Charles K. , Vickers Thomas J. , Womack James D.
Published: July 2005

The problems encountered in applying Raman spectroscopy to direct qualitative and quantitative analysis for minor impurities in nominally pure, colorless solids have been examined. Samples of sulfamethoxazole spiked with 0.5 to 5% of sulfanilamide and sulfanilic acid were used as test materials. A procedure is described which permits detection of spectral features of the specified impurities at the 0.5% level. Least-squares fitting and cross-correlation data treatment procedures for the determination of sulfanilamide in sulfamethoxazole, with limits of detection of about 0.1% for either approach, are described. Computer simulations have been used to examine detection of impurity peaks for a variety of conditions, including the worst-case scenario in which the impurity features coincide with the strongest features of the spectrum of the host material. A least-squares fitting approach is described which permits detection of the impurity peak at the 0.5% level, even under worst case conditions.
Detection of Methanol in Gasolines Using Near-Infrared Spectroscopy and an Optical Fiber
Authors: Buchanan B. R. , Honigs D. E.
Published: July 2005

Because of methanol's relatively low cost and its utility as an octane booster, a need to monitor the concentration of methanol in gasolines has evolved. Near-infrared analysis can be used to monitor methanol in gasolines with the use of optical fiber. If stepwise multiple linear regression is used, methanol can be predicted to within 0.25 weight percent. The use of an optical fiber lowers personnel and instrument exposure to hazardous environments and minimizes the risk of explosion. It is pointed out, however, that care must be taken in the prediction of future specimens. The differences between enumerative and analytical calibrations are also discussed.
FT-IR Technique for Monitoring the Interfacial Interactions of a Surfactant Solution and a Solid Hydrocarbon
Authors: Scheuing David R.
Published: July 2005

A cylindrical internal reflection element (IRE) has been used as a support for a solid hydrocarbon-aqueous nonionic surfactant interface. Time-resolved FT-IR spectra of the interface during the removal of the hydrocarbon from the IRE surface by the detergent action of flowing surfactant solutions have been recorded. Qualitative comparisons of the detergency of different surfactants can be made. With the use of subtraction techniques, the spectra of interfacially adsorbed and aqueous surfactant can be obtained for comparison. Significant adsorption of a relatively hydrophobic ethoxylated alcohol (Neodol 25–3) at the interface was detected. The ether group bands of the adsorbed surfactant were different from those in the spectrum of an aqueous dispersion of the surfactant. The removal of hydrocarbon from the IRE by the Neodol 25–3 was much slower than that caused by a more hydrophilic material, Neodol 23–6.5.
Dynamic Range Problems in Fourier Transform IR and Far-IR Spectroscopy
Authors: Hoffmann Pedro , Knözinger Erich
Published: July 2005

The exploitation of both the multiplex and the aperture advantage in Fourier transform IR and far-IR spectroscopy may lead to nonlinear detector response or saturation of the A/D converter. This limitation of the dynamic range only concerns the center-burst peak of the interferogram function. After the Fourier transformation, the respective distortion in the frequency or—better—wavenumber domain is completely delocalized. Erroneous intensity contributions are, in principle, present in all parts of the spectrum under consideration. Thus, it is not easy to diagnose the effect of a limited dynamic range. Practical procedures for the recognition and elimination of the respective artifacts in the spectrum are, therefore, suggested; they are to be used in conjunction with the application of the IR transmission technique to surface studies of high-surface-area SiO2.
Lifetime Measurement by Using the Laplace Transform in Single-Photon-Decay Spectroscopy
Authors: Moreno F. , LÓPez R. J.
Published: July 2005

In this paper we present a method for processing the time-interval data obtained in a single-photon-decay spectroscopy experiment. This method is based on the measurement of the Laplace transform of Pƒ( t) [the probability distribution function of the time of arrival of the first photon (PDFP) after the excitation pulse] instead of the direct measurement of Pƒ( t) by means of a multichannel analyzer. With the use of this method, a good estimation of the lifetime of the signal can be obtained with a shorter measurement time than that used in the conventional method, in which the recorded time intervals are used to construct Pƒ( t). A theoretical model of the error involved in determining the lifetime is obtained for the Laplace method, and it is compared with that corresponding to the measurement of Pƒ( t) by means of a multichannel analyzer. Finally, a computer simulation of the experiment is performed to corroborate the theoretical predictions.
FT-IR Study of Ester Solubilization into a Micelle Solution
Authors: Hayakawa Shinjiro , Matsui Tomoko , Tanaka Shigeyuki
Published: July 2005

The existence of phenyl acetate and benzyl acetate solubilized into a sodium decanoate micelle solution was studied by Fourier transform infrared spectroscopy. When the spectra of acetates in a micelle solution are compared with those in CCl4, the vC=O and vasC-O regions of acetates in the micelle solution show great changes, such as band splitting, lower peak shifts, and band broadening. The lower shifts and the band broadening of vC=O indicate that acetates are solubilized into the surface polar layer of the micelle and are affected by hydrogen bonding. The solubilized volume of acetates in the micelle solution was varied, and the dependence of the peak position and the intensity of the vC=O region was examined. Assuming that the peak position represents the environment of the carbonyl group, there are two kinds of environments around the acetates. Most of acetates are in a polar environment, but when the acetates in the micelle come close to saturation, some of them are in a nonpolar environment. The vasC-O region of benzyl acetate in a micelle solution shows a complex band shape, compared with that of phenyl acetate. The asymmetric C-O mode is a skeleton mode and is sensitive to conformational changes. The polar environment around benzyl acetate may make conformational changes in the benzyl acetate.
Sheath Flow Jet Expansions of Liquids and Supercritical Fluids
Authors: Anderson Bruce D. , Johnston Murray V.
Published: July 2005

A method is described for performing supersonic jet spectroscopy of compounds dissolved in a liquid or supercritical fluid. The fluid is expanded through a capillary restrictor into a concentric sheath gas flow of argon. The resulting mixture undergoes further expansion through a 200-μm tapered nozzle. Laser-induced fluorescence of naphthalene is used to probe the cooling and focusing properties of the nozzle. A rotational temperature of 12 K has been obtained for a variety of fluid carriers. No fluorescence enhancement is observed along the centerline of the expansion relative to the results with a conventional free jet expansion.