Detection of Aliphatically Bridged Multi-Core Polycyclic Aromatic Hydrocarbons in Sooting Flames with Atmospheric-Sampling High-Resolution Tandem Mass Spectrometry.

This paper provides experimental evidence for the chemical structures of aliphatically substituted and bridged polycyclic aromatic hydrocarbon (PAH) species in gas-physe combustion environments. The identification of these single- and multicore aromatic species, which have been hypothesized to be important in PAH growth and soot nucleation, was made possible through a combination of sampling gaseous constituents from an atmospheric pressure inverse coflow diffusion flame of ethylene and high-resolution tandem mass spectrometry (MS-MS). In these experiments, the flame-sampled components were ionized using a continuous VUV lamp at 10.0 eV and the ions were subsequently fragmented through collisions with Ar atoms in a collision-induced dissociation (CID) process. The resulting fragment ions, which were separated using a reflectron time-of-flight mass spectrometer, were used to extract structural information about the sampled aromatic compounds. The high-resolution mass spectra revealed the presence of alkylated single-core aromatic compounds and the fragment ions that were observed correspond to the loss of saturated and unsaturated units containing up to a total of 6 carbon atoms. Furthermore, the aromatic structures that form the foundational building blocks of the larger PAHs were identified to be smaller single-ring and pericondensed aromatic species with repetitive structural features. For demonstrative purposes, details are provided for the CID of molecular ions at masses 202 and 434. Insights into the role of the aliphatically substituted and bridged aromatics in the reaction network of PAH growth chemistry were obtained from spatially resolved measurements of the flame. The experimental results are consistent with a growth mechanism in which alkylated aromatics are oxidized to form pericondensed ring structures or react and recombine with other aromatics to form larger, potentially three-dimensional, aliphatically bridged multicore aromatic hydrocarbons.

Retinal shows its true colours: photoisomerization action spectra of mobility-selected isomers of the retinal protonated Schiff base.

Retinal is one of Nature's most important and widespread chromophores, exhibiting remarkable versatility in its function and spectral response, depending on its protein environment. Reliable spectroscopic and photochemical data for the isolated retinal molecule are essential for calibrating theoretical approaches that seek to model retinal's behaviour in complex protein environments. However, due to low densities and possible co-existence of multiple isomers, retinal is a challenging target for gas-phase investigations. Here, the photoisomerization behaviour of the trans isomer of the retinal protonated Schiff base (RPSB) is investigated in the gas phase by irradiating mobility-selected RPSB ions with tunable light in a tandem ion mobility spectrometer. trans RPSB ions are converted to single cis isomers and also more compact isomers through irradiation with visible light. The S1← S0 photoisomerization action spectrum of trans RPSB, obtained by monitoring production of cis isomers as a function of wavelength, exhibits a single well-defined peak with a maximum at 618 ± 5 nm. Corresponding action spectra of cis RPSB isomers exhibit broader peaks, conclusively demonstrating an isomeric dependence for the RPSB spectrum in the gas phase.

Photoisomerization action spectrum of retinal protonated Schiff base in the gas phase.

The photophysical behaviour of the isolated retinal protonated n-butylamine Schiff base (RPSB) is investigated in the gas phase using a combination of ion mobility spectrometry and laser spectroscopy. The RPSB cations are introduced by electrospray ionisation into an ion mobility mass spectrometer where they are exposed to tunable laser radiation in the region of the S1 ← S0 transition (420-680 nm range). Four peaks are observed in the arrival time distribution of the RPSB ions. On the basis of predicted collision cross sections with nitrogen gas, the dominant peak is assigned to the all-trans isomer, whereas the subsidiary peaks are assigned to various single, double and triple cis geometric isomers. RPSB ions that absorb laser radiation undergo photoisomerization, leading to a detectable change in their drift speed. By monitoring the photoisomer signal as a function of laser wavelength an action spectrum, extending from 480 to 660 nm with a clear peak at 615 ± 5 nm, is obtained. The photoisomerization action spectrum is related to the absorption spectrum of isolated retinal RPSB molecules and should help benchmark future electronic structure calculations.

What happens post-pilot testing? A model for revising a disability awareness and competency training program.

Disability awareness and competency trainings are an important component of addressing ableism and health equity in the health promotion context. This commentary describes our process of developing, implementing, and refining a disability competency training, the Inclusive Community Exercise Training, for community-based group exercise instructors. The training originated from a partnership between academic researchers, community organizations, and individuals with disabilities. After initial pilot testing, we used feedback from participants to enhance the training. To optimize successful dissemination of this training, we utilized the Reach, Effectiveness, Adoption, Implementation, and Maintenance (RE-AIM) framework, which is widely used in public health. The revision process focused on generalizing content to suit a wider audience, utilizing an eLearning platform for dissemination, and optimizing interactivity to improve learning effectiveness. The commentary emphasizes the lessons learned and the significance of systematic program revision, considering diverse expertise, content tailoring, and the benefits of accessible eLearning platforms.

Changing the shape of molecular ions: photoisomerization action spectroscopy in the gas phase.

A new approach for studying the photoisomerization of molecular ions in the gas phase is described. Packets of molecular ions are injected into a drift tube filled with helium buffer gas, where they are irradiated with tunable laser light. Photoisomerization changes the ions' cross section for collisions with helium atoms so that they arrive at the ion detector slightly earlier or later than the parent ions. By monitoring the photo-isomer peak as a function of laser wavelength one can record an action spectrum that is related to the ions' absorption spectrum modulated by the photoisomerization probability. The approach is demonstrated using the polymethine dye HITC (1,3,3,1',3',3'-hexamethylindotricarbocyanine). The data show that both trans and cis forms of HITC(+) exist in the gas phase with trans→cis photoisomerization predominating over the 550-710 nm range and cis→trans photoisomerization occurring over the 735-770 nm range. The gas-phase photoisomerization action spectrum is comparable to the absorption spectra of trans HITC and cis HTIC in the condensed phase, but with the absorption peaks shifted to shorter wavelength. The gas-phase photoisomerization action spectrum of the (HITC)2(2+) dication dimer is also reported. (HITC)2(2+) cations photoisomerize over the 550-770 nm range to form more compact structures.

Ethanol photo-oxidation on a rutile TiO2(110) single crystal surface.

The reaction of ethanol has been studied on the surface of rutile TiO(2)(110) by Temperature Programmed Desorption (TPD), online mass spectrometry under UV excitation and photoelectron spectroscopy while the adsorption energies of the molecular and dissociative modes of ethanol were computed using the DFT/GGA method. The most stable configuration is the dissociative adsorption in line with experimental results at room temperature. At 0.5 ML coverage the adsorption energy was found equal to 80 kJ mol(-1) for the dissociative mode (ethoxide, CH(3)CH(2)O(a) + H(a)) followed by the molecular mode (67 kJ mol(-1)). The orientation of the ethoxides along the [001] or [110] direction had minor effect on the adsorption energy although affected differently the Ti and O surface atomic positions. TPD after ethanol adsorption at 300 K indicated two main reactions: dehydration to ethylene and dehydrogenation to acetaldehyde. Pre-dosing the surface with ethanol at 300 K followed by exposure to UV resulted in the formation of acetaldehyde and hydrogen. The amount of acetaldehyde could be directly linked to the presence of gas phase O(2) in the vacuum chamber. The order of this photo-catalytic reaction with respect to O(2) was found to be 0.5. Part of acetaldehyde further reacted with O(2) under UV excitation to give surface acetate species. Because the rate of photo-oxidation of acetates (acetic acid) was slower than that of ethoxides (ethanol), the surface ended up by being covered with large amounts of acetates. A reaction mechanism for acetaldehyde, hydrogen and acetate formation under UV excitation is proposed.

People with MS are less physically active than healthy controls but as active as those with other chronic diseases: An updated meta-analysis.

BACKGROUND: There has been remarkable growth in research examining physical activity behavior (any bodily movement produced by skeletal muscle contraction that results in energy expenditure) among people living with multiple sclerosis (MS) over the past decade. The current meta-analysis quantified physical activity participation levels in persons with MS compared with non-diseased and other clinical populations. METHODS: We searched PUBMED, PsycINFO and Web of Science using the keywords physical activity, exercise, and physical fitness in conjunction with MS. We conducted a quantitative synthesis of the difference in physical activity participation levels among persons with MS compared with non-diseased populations and other clinical populations and then examined moderators that might explain variation in the overall effect size (ES). RESULTS: 21 studies were included involving 5303 persons with MS and yielded a mean ES of -0.57 (95% CI=-0.76, 60.37). The weighted mean ES was heterogeneous (Q=443.811, df=31, p<0.001). The magnitude of the mean ES increased when comparing the MS population with non-diseased populations, but decreased when comparing MS with clinical populations. CONCLUSION: The cumulative evidence reinforces that persons with MS are less physically active than non-diseased, but not clinical populations, and this observation supports the need for new efforts on promoting physical activity across the MS community.

Crafty birds and fitness fiends: relationships of professional and leisure activities.

Stereotypes of therapists were found to contain a 'kernel of truth' in a survey comparing the active and passive leisure pursuits of female physiotherapy (N = 100) and occupational therapy (N = 107) graduates and undergraduates. Physiotherapists had relatively more active leisure patterns as adolescents and undergraduates. Occupational therapists had relatively passive leisure patterns that persisted after graduation. These findings support the spillover hypothesis of a work-leisure relationship. Following graduation physiotherapists adopted more passive leisure pursuits which supports the compensation theory of leisure. However, physiotherapy graduates felt deprived of sport and experienced less leisure satisfaction than occupational therapists.

Medicine and the health professions: issues of dominance, autonomy and authority.

Medical dominance of health care has traditionally been the organising principle in health care delivery. Medical power is manifested through the professional autonomy of doctors, through their pivotal role in the economics of health services, through dominance over allied health occupational groups, through administrative influence, and through the collective influence of medical associations. Using Friedson's four factor definition of medical dominance, a structured interview schedule was developed to examine one aspect of medical dominance, that is, doctors' control over the allied health professions. Ninety interviews were carried out with a sample of nurses, physiotherapists, occupational therapists, speech pathologists and psychologists working in various health care settings in metropolitan Sydney, seeking their perceptions on the way in which the medical profession interacts with their occupational group. The findings indicate that a significant proportion (73%) of health professionals did not feel regarded as professional equals by doctors. Nor did they feel that doctors had an adequate knowledge and understanding of their professions (73%). However, the majority (74%) felt that they had sufficient autonomy and were able to discuss doctors' instructions and offer advice or suggestions to doctors. Length of service significantly contributed to perceptions of professional autonomy amongst allied health professionals. These results support the view that the increased autonomy of the allied health professions has not impinged on medical dominance in the health care delivery system. Recommendations for further research and the training of medical and allied health professionals are made.

Health personnel: perceived differences in professional relationships and work role.

This study questions the validity of the assumption that the workplace culture and experiences of health personnel are largely similar. The study compares nurses, occupational therapists, physiotherapists and speech therapists concerning their perceptions of professional issues within their own profession, and their perceptions of professional issues within the medical profession. Respondents completed a questionnaire containing 55 items referring to their own profession, and 55 items referring to the medical profession. Six scales were derived from the large survey instrument addressing issues regarding status/cohesiveness of the profession, professional relationships, and the role of the patient in health delivery in the respondent's profession, and in the medical profession. Nurses emerged as different to other health personnel on most dimensions. Few differences emerged among allied health professionals. Physiotherapists were more positive than occupational therapists about the status/cohesiveness of their profession, and regarded the contributions of the patient to health delivery as less important. Speech therapists did not differ significantly from occupational therapists on any dimension.

Coping with stress in the workplace: implications for new health professionals.

Because health care professionals must provide high-quality care while simultaneously adjusting to the new demands of a rapidly changing health care system, work stress and possibly even burnout are prevalent issues for both senior professionals and recent health science graduates upon entry into the workforce. This article examines the experience of stress and the importance of coping abilities, particularly focusing on students enrolled in health professional courses and those who have recently entered the workforce. It also presents research pertaining to whether newly graduated health professionals are coping effectively with the demands of work. Suggestions for improving stress-coping abilities are given.

Australian physiotherapists' and occupational therapists' views on professional practice.

The extent to which physiotherapists and occupational therapists endorse a humanistic, holistic approach to health care was addressed in a survey of attitudes of practicing occupational therapists (N = 378) and physiotherapists (N = 558). A 22-item questionnaire including aspects of therapist's knowledge and techniques, holistic approach, client characteristics, client/therapist relationship, and approaches to professional practice was employed. The findings indicate that the professional practices reflecting the new public health model prevailed. This model emphasizes client/therapist interaction, the client's own ability to change and improve, and holistic attitudes towards health care, along with the therapist's knowledge and skills. However, comparative analyses of the two therapy groups reveal that although both groups support a humanistic approach to client care, occupational therapists promote the client's resources and coping skills to a greater extent, place more emphasis on the client in terms of the client's capacity for recovery and coping abilities, were more involved with the social, personal, and psychological problems of the client, and place less emphasis on treatment methods and techniques than physiotherapists. Demographic variables including gender, age, and workplace setting (public/private) were found to be significantly related to views of professional practice. Recommendations for the training of therapists and the implications for practitioners are made and suggestions for further research are given.

An analysis of managerial skills for the current and future health care environment.

A survey questioned 503 experienced practitioners about managerial tasks and responsibilities of senior professionals in four allied health fields: physiotherapy, speech-language pathology, occupational therapy, and medical radiation science. Participants worked in a range of settings, including the private and public sectors, small and large departments/units, and community and hospital-based work sites. Factor analysis identified eight managerial areas of functioning: department running, staff relations management, legislative knowledge, career path management, implementation and change, quality assurance, management of future planning, and prioritizing work. The professional field of the practitioner influenced the importances attached to these areas, while work setting and gender of practitioner had minimal impact. Level of involvement in managerial tasks had no bearing on the importance attached to competency areas. Open-ended comments added depth to the results of the factor analysis. The findings are discussed with respect to the changing requirements being placed upon health service personnel.

The creation of strategic alliances: the experience of the London Health Sciences Centre and southwestern Ontario.

This article describes the framework and strategies that the London Health Sciences Centre has developed to foster trusting and collaborative relationships with its regional partners in Southwestern Ontario. A four-phase approach was used to identify, implement and evaluate system-wide opportunities to improve the integration of clinical care in Southwestern Ontario. Specific case studies are illustrated that used this framework to improve both access to patient services and length of stay, while positively affecting operating resources.

Health science graduates: preparation for the workplace.

The research reported in this article was undertaken to assess the perceptions of health science graduates in the fields of health information management, occupational therapy, orthoptics, physiotherapy, and speech pathology regarding their perceptions of the adequacy of undergraduate preparation in meeting the demands of a changing health care environment. An instrument was devised for use by graduates on the basis of the skills and workplace behaviours specified by experienced practitioners in the above fields as necessary in newly recruited graduates. A total of 527 health science graduates completed the 52 item instrument. The statistical analyses indicated that 11 factors define the adequacy of graduates' preparation for the workplace. Health science graduates perceived themselves to have been more thoroughly prepared on certain workplace dimensions than on others. Specifically, graduates perceived themselves to be ill-equipped on dimensions concerned with workplace management, knowledge of the health industry, and coping in the workplace. Graduates also perceived themselves to be inadequately prepared in terms of communicating with clients, health professionals, and the general public. The strengths of their courses were perceived to be in completing essential tasks, having confidence in the clinical role, in ethical practice, in pursuit and application of knowledge, and having a realistic expectation of the workplace role. The results are discussed in terms of the need to address curriculum changes.

Impact of curricular change in an undergraduate program for speech pathologists on perceived preparedness for the workplace.

Recently, educational policymakers have emphasized the need for undergraduate programs to develop in their graduates generic skills and attributes beyond discipline-specific skills and knowledge. The generic skills and attributes should mesh with the requirements of the workplaces where the graduates will find employment. The present study examined the impact of curricular revisions to a program of study for speech pathologists on the perceptions of the graduates regarding their preparation in appropriate skill and knowledge domains. The curricular revisions sought to develop independent learning, critical thinking, research and evaluation skills, written and oral communication skills, and skills for seeking and providing support to peers. Seventy-eight graduates of the earlier program and 21 graduates of the revised program offered by the School of Communication Disorders at The University of Sydney completed a 52-item questionnaire concerning the extent to which the program had equipped them for the workplace. Eleven scales were derived from the questionnaire responses, reflecting skills endorsed by university educators and workplace supervisors of allied health professionals as being necessary for success in the workplace. The relative levels of perceived preparation on the 11 dimensions were similar across graduates of the revised program and those of the earlier program. Graduates of the revised program were significantly more positive about their preparation on five of the 11 dimensions, compared with earlier graduates of approximately equivalent age and experience. The dimensions where differences were observed generally reflected those targeted by the curricular revisions.

Australian speech pathologists' views of what professional practices lead to successful outcomes of therapy.

The relative importance attributed to factors perceived by speech pathologists as contributing to successful levels of therapeutic outcomes were addressed in a survey of 372 practicing therapists in Australia. The survey consisted of 42 items derived from interviews with a sample of ten speech pathologists in Sydney. Therapists were asked to rate the importance of each item on a seven-point scale ranging from "not at all important" to "critically important." The findings indicate that the most important ingredients of successful therapy incorporate a mix of support and therapeutic activity outside the clinic; the clinicians' organizational skills and involvement in conducting therapy and their use of techniques; the positive therapeutic relationship between clinician and client; and, finally, the client's attitude to therapy. These findings suggest that speech pathologists, like other allied health professionals, endorse a humanistic or holistic approach to health care. The results provide insights into the practices that should be addressed and fostered in undergraduate speech pathology programs.

The creation of a profession leader role in an academic health sciences centre.

The introduction and administration of any new role in a dynamic changing environment requires strong leadership and specific, purposeful administrative strategies. This article describes the development of a professional leader role at one campus of a recently merged academic health sciences centre. Understanding the operational challenges may help other healthcare organizations that wish to introduce and refine professional leadership roles.

Ion Mobility Unlocks the Photofragmentation Mechanism of Retinal Protonated Schiff Base.

Retinal protonated Schiff base (RPSB) is a key molecular component of biological photoreceptors and bacterial photosynthetic structures, where its action involves photoisomerization around bonds in the polyene chain. In a vacuum environment, collisional activation or exposure to visible light causes the RPSB molecule to disintegrate, producing charged molecular fragments with m/z = 248 Da that cannot be formed by simple cleavage of the polyene chain. Photofragments resulting from laser excitation of RPSB at a wavelength of 532 nm are analyzed in an ion mobility mass spectrometer (IMMS) and found to be the protonated Schiff base of ß-ionone. Density functional theory calculations at the M06-2X/cc-pVDZ level support a fragmentation mechanism in which RPSB undergoes an electrocyclization/fragmentation cascade with the production of protonated Schiff base of ß-ionone and toluene.