871 resultados para Employment of funds


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Notwithstanding advances in modern chemical methods, the selective installation of sterically encumbered carbon stereocenters, in particular all-carbon quaternary centers, remains an unsolved problem in organic chemistry. The prevalence of all-carbon quaternary centers in biologically active natural products and pharmaceutical compounds provides a strong impetus to address current limitations in the state of the art of their generation. This thesis presents four related projects, all of which share in the goal of constructing highly-congested carbon centers in a stereoselective manner, and in the use of transition-metal catalyzed alkylation as a means to address that goal.

The first research described is an extension of allylic alkylation methodology previously developed in the Stoltz group to small, strained rings. This research constitutes the first transition metal-catalyzed enantioselective α-alkylation of cyclobutanones. Under Pd-catalysis, this chemistry affords all–carbon α-quaternary cyclobutanones in good to excellent yields and enantioselectivities.

Next is described our development of a (trimethylsilyl)ethyl β-ketoester class of enolate precursors, and their application in palladium–catalyzed asymmetric allylic alkylation to yield a variety of α-quaternary ketones and lactams. Independent coupling partner synthesis engenders enhanced allyl substrate scope relative to allyl β-ketoester substrates; highly functionalized α-quaternary ketones generated by the union of our fluoride-triggered β-ketoesters and sensitive allylic alkylation coupling partners serve to demonstrate the utility of this method for complex fragment coupling.

Lastly, our development of an Ir-catalyzed asymmetric allylic alkylation of cyclic β-ketoesters to afford highly congested, vicinal stereocenters comprised of tertiary and all-carbon quaternary centers with outstanding regio-, diastereo-, and enantiocontrol is detailed. Implementation of a subsequent Pd-catalyzed alkylation affords dialkylated products with pinpoint stereochemical control of both chiral centers. The chemistry is then extended to include acyclic β-ketoesters and similar levels of selective and functional group tolerance are observed. Critical to the successful development of this method was the employment of iridium catalysis in concert with N-aryl-phosphoramidite ligands.

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Blue ray optical storage is one of the important trends in the area of information storage, and attracts a number of researchers. Static tester for blue ray optical storage plays an important role in storage media research. We designed and constructed a static tester, in which modularization makes it very convenient to expand function. Employment of modulation/demodulation technique weakens test error so as to increase test precision. Focus move mode and the nano-positioners facilitate the relocation of recording marks. Only one laser with wavelength 406.7 nm is used. In this paper, system design and characteristics are represented in detail, and some experimental results are also given to show that the static tester can perform successfully, acting as research platform for blue ray optical storage. (c) 2005 Elsevier GmbH. All rights reserved.

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Fish play a crucial role in the Bangladeshi diet, providing more than 60% of animal source food, representing a crucial source of micro-nutrients, and possessing an extremely strong cultural attachment. Fish (including shrimp and prawn) is the second most valuable agricultural crop, and its production contributes to the livelihoods and employment of millions. The culture and consumption of fish therefore has important implications for national food and nutrition security, poverty and growth. This review examines the current state of knowledge on the aquaculture sector and fish consumption in Bangladesh, based on extensive analysis of secondary sources (including unpublished data unavailable elsewhere), consultation with various experts and specially conducted surveys.

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The Lower Mekong Basin has extensive wetlands and these are being threatened by numerous problems. Most of these problems are interdependent and interact with one another. The lack of an appropriate definition of wetlands applicable to the region, pervasive inefficiencies and chronic lack of funds among riparian governments, and the poor appreciation of the true economic importance of wetlands and its resources are among the most prominent. The current definition, based on the Convention on Wetlands (Ramsar, Iran, 1971), is too broad when compared to the understanding of wetlands as being swamps, marshes and the like, and was developed specifically for wetlands with international importance as waterfowl habitats. Furthermore, wetlands are composed of different types of resources, which require different modes of management. Often, institutional competition, overlapping mandates and sometimes jealousies occur between government departments when they try to assert their authority on a particular wetland resource and use, and put forward their development plans without considering how these may conflict with other wetlands uses. Finally, effective wetland management requires reliable statistics or information on rate of harvest of natural resources such as fish and others, fishing/harvesting methods over time in order to determine the level of exploitation, and the status of the natural resources. This information is needed to identify opportunities for expansion, to establish historical trends, and to determine when management interventions are necessary to protect the resources from being overused by other developments. In order to address these issues, ICLARM - The World Fish Center has launched a project, the aim of objectives of which are described in this paper.

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This thesis details the design and implementation of novel chemical routes towards a series of highly propitious 7-azaindolyl derivatives of the indolocarbazole (ICZ) and bisindolylmaleimide (BIM) families, with subsequent evaluation for use as cancer chemotherapeutic agents. A robust synthetic strategy was devised to allow the introduction of a 7-azaindolyl moiety into our molecular template. This approach allowed access to a wide range of β-keto ester and β-keto nitrile intermediates. Critical analysis identified F-ring modulation as a major theme towards the advancement of ICZ and BIM derivatives in drug therapy. Thus, the employment of cyclocondensation methodology furnished a number of novel aminopyrazole, isoxazolone, pyrazolone and pyrimidinone analogues, considerably widening the scope of the prevalent maleimide functionality. Photochemical cyclisation provided for the first reported aza ICZ containing a six-membered F-ring. Another method towards achieving the aza ICZ core involved use of a Perkin-type condensation approach, with chemical elaboration of the headgroup instigated post-aromatisation. Subsequent use of a modified Lossen rearrangement allowed access to further analogues containing a six-membered F-ring. Extensive screening of the novel aza ICZ and BIM derivatives was carried out against the NCI-60 cancer cell array, with nine prospective candidates selected for continued biological evaluation. From these assays, a number of compounds were shown to inhibit cancer cell growth at concentrations of below 10 nM. Indeed, the most active aza ICZ tested is currently under assessment by the Biological Evaluation Committee of the NCI due to excellent antiproliferative activity demonstrated across the panel of cell lines, with a mean GI50 of 34 nM, a mean total growth inhibition (TGI) of 4.6 μM and a mean cytotoxicity (LC50) of 63.1 μM. Correlation to known topoisomerase I (topo I) inhibitors was revealed by COMPARE analysis, and subsequent topo I-mediated DNA cleavage assays showed inhibitory activity below 1 μM for several derivatives.

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The advent of modern wireless technologies has seen a shift in focus towards the design and development of educational systems for deployment through mobile devices. The use of mobile phones, tablets and Personal Digital Assistants (PDAs) is steadily growing across the educational sector as a whole. Mobile learning (mLearning) systems developed for deployment on such devices hold great significance for the future of education. However, mLearning systems must be built around the particular learner’s needs based on both their motivation to learn and subsequent learning outcomes. This thesis investigates how biometric technologies, in particular accelerometer and eye-tracking technologies, could effectively be employed within the development of mobile learning systems to facilitate the needs of individual learners. The creation of personalised learning environments must enable the achievement of improved learning outcomes for users, particularly at an individual level. Therefore consideration is given to individual learning-style differences within the electronic learning (eLearning) space. The overall area of eLearning is considered and areas such as biometric technology and educational psychology are explored for the development of personalised educational systems. This thesis explains the basis of the author’s hypotheses and presents the results of several studies carried out throughout the PhD research period. These results show that both accelerometer and eye-tracking technologies can be employed as an Human Computer Interaction (HCI) method in the detection of student learning-styles to facilitate the provision of automatically adapted eLearning spaces. Finally the author provides recommendations for developers in the creation of adaptive mobile learning systems through the employment of biometric technology as a user interaction tool within mLearning applications. Further research paths are identified and a roadmap for future of research in this area is defined.

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Conflicts of interests have long been recognized as potential sources of influence in the conduct and reporting of clinical trials. This controversy was again rekindled after the publication of the latest statin guidelines and a series of studies regarding competing interests in leading medical journals. We investigate the association between declared author conflicts and the outcomes of large cardiovascular trials. We searched the Medline (PubMed) database to identify "phase 2" and "phase 3" clinical trials using the search term "cardiovascular" over the past decade using "10 years" as the filter. We perceived the competing interest as present regardless of the nature such as consulting fees, honoraria, travel imbursements, stock holding, and employment. Of the 699 titles retrieved, 114 studies met the inclusion criteria. Nearly 80% of studies had at least a single author with competing interests. The 114 studies had a total of 1,433 investigators, of which 725 had declared conflicts of interests (50.6%). A total of 66 studies (58%) had half or >50 percent of investigators who had some conflicts of interests. Of these studies, 54 studies had favorable outcomes and only 12 had unfavorable outcomes (p <0.001). Among the type of competing interests, consulting or personal fees was the most common present in 58 investigators (51%). This was followed by research grants present in 55 the researchers (48%). Among 25 (22%) studies, at least one investigator reported stakes in the industry, of which only 2 studies had unfavorable outcomes for the intervention being investigated. Just 1 of the 25 clinical trials with a sample size of >1,000 had no investigators with competing interests. In conclusion, authors conflicts are associated with favorable outcomes in cardiovascular outcome trials.

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The objective of this cross-sectional study was a comprehensive nutrition and health assessment to provide a basis for future intervention strategies for an elderly population attending a day-care centre. Socio-demographic, health and 24-hour recall dietary intake questionnaires were administered and anthropometric and biochemical measurements taken. The results indicate that the majority of respondents had an income of between R501 and R1 000 (South African rand) per month and most of them reported an occasional lack of funds to meet basic household needs, confirming the presence of food insecurity. Daily dietary intakes (mean [+ or -] Standard Deviation [SD]) of the women were 5 395 [+ or -] 2 946 kJ energy, 47 [+ or -] 27 g protein, 28 [+ or -] 21 g fat and 196 [+ or -] 123 g carbohydrates compared to 8 641 [+ or -] 3 799 kJ, 86 [+ or -] 48 g, 49 [+ or -] 32 g and 301 [+ or -] 139 g of the men, respectively. The majority (83.6%) of the women were overweight (body mass index [BMI] [greater than or equal to] 25) or obese (BMI [greater than or equal to] 30) whilst 78% had a mid-upper arm circumference (MUAC) of [greater than or equal to] 21.7 cm. Mean intakes of micronutrients were low in comparison to reference standards and serum zinc levels were suboptimal. Obesity, hypertension and raised total serum cholesterol levels indicated an increased risk for coronary heart disease. It can be concluded that a low income, household food insecurity and risk factors associated with malnutrition and non-communicable diseases were prevalent in this elderly population. OPSOMMING Die doelwit van hierdie dwarssnitstudie was ‘n omvattende bepaling van voeding- en gesondheidstatus om as basis te dien vir toekomstige intervensiestrategieë vir ’n groep bejaardes wat ’n dagsentrum besoek. Sosiodemografiese, gesondheid- en 24-uur herroep-dieetinname vraelyste is voltooi en antropometriese en biochemiese metings is geneem. Die resultate het bevestig dat die meerderheid respondente ‘n maandelikse inkomste van tussen R501 en R1 000 (Suid-Afrikaanse rand) gehad het. Die meeste het ‘n geldtekort vir basiese huishoudelike behoeftes gerapporteer wat dui op huishoudelike voedselinsekuriteit. Daaglikse dieetinnames (gemiddeld±standaardafwyking [SA]) van die vroue was onderskeidelik 5 395±2 946 kJ energie, 47±27 g proteïen, 28±21 g vet en 196±123 g koolhidrate in vergelyking met 8 641±3 799 kJ, 86±48 g, 49±32 g en 301±139 g vir die mans. Die meerderheid (83.6%) van die vroue was oorgewig (liggaamsmassa-indeks [LMI] >25) of vetsugtig (LMI > 30) en 78% het ’n middel-bo-armomtrek (MUAC) van > 21.7 cm gehad. Gemiddelde mikronutriëntinnames was laag in vergelyking met die verwysingstandaarde en serumsink was suboptimaal. Vetsug, hipertensie en verhoogde totale serumcholesterolvlakke het op ‘n verhoogde risiko van kardiovaskulêre siekte gedui. Die resultate het dus bewys dat lae inkomste, huishoudelike voedselinsekuriteit en die risikofaktore wat met wanvoeding en leefstylsiektes geassosieer word, teenwoordig was.

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The effectiveness of corporate governance mechanisms has been a subject of academic research for many decades. Although the large majority of corporate governance studies prior to mid 1990s were based on data from developed market economies such as the U.S., U.K. and Japan, in recent years researchers have begun examining corporate governance in transition economies. A comparison of China and India offers a unique environment for analyzing the effectiveness of corporate governance. First, both countries state-owned enterprise (SOE) reform strategies hinges on the Modern Enterprise System characterized by the separation of ownership and control. Ownership of an SOE’s assets is distributed among the government, institutional investors, managers, employees, and private investors. Effective control rights are assigned to management, which generally has a very small, or even nonexistent ownership stake. This distinctive shareholding structure creates conflict of interest not only between management (insiders) and outside investors but also between large shareholders and minority investors. Moreover, because both governments desire to retain some control—in part through partial retained ownership of commercialized SOEs, further conflicts arise between politicians and firms. Second, directors in publicly listed firms in both countries are predominantly drawn from institutions with significant non-market objectives: the government and other state enterprises, particularly in China, and extended families, particularly in India. As a result, the effectiveness of internal governance mechanisms, such as the number of independent directors on the board and the number of independent supervisors on the supervisory committee, are likely to be quiet limited, although this has yet to be fully evaluated. Third, because of the political nature of the privatization process itself, typical external governance mechanisms, such as debt (in conjunction with appropriate bankruptcy procedures), takeover threats, legal protection of investors, product market competition, etc., have not been effective. Bank loans have traditionally been viewed as grants from the state designed to bail out failing firms. State-owned banks retain monopoly or quasi-monopoly positions in the banking sector and profit is not their overriding objective. If political favor is deemed appropriate, subsidized loans, rescheduling of overdue debt or even outright transfer of funds can be arranged with SOEs (soft budget constraints). In addition, a market for private, non-bank debt is limited in India and has yet to be established China. There is no active merger or takeover activity in Chinese stock markets to discipline management. Information available in the capital markets is insufficient to keep at arm’s length of the corporate decisions. In light of the above peculiarities, China and India share many of the typical institutional characteristics as a transition economy, including poor legal protection of creditors and investors, the absence of an effective takeover market, an underdeveloped capital market, a relative inefficient banking system and significant interference of politicians in firm management. Su (2005) finds that the extent of political interference, managerial entrenchment and institutional control can help explain corporate dividend policies and post-IPO financing choices in this situation. Allen et al. (2005) demonstrate that standard corporate governance mechanisms are weak and ineffective for publicly listed firms while alternative governance mechanisms based on reputation and relationship have been remarkably effective in the private sector. Because the peculiarities are significant in this context, the differences in the political-economies of the two countries are likely to be evident in such relational terms. In this paper we explore the peculiarities of corporate governance in this transitional environment through a systematic examination of certain aspects of these reputational and relationship dimensions. Utilising the methods of social network analysis we identify the inter-organisational relationships at board level formed by equity holdings and by shared directors. Using data drawn from the Orbis database we map these relations among the 3700 largest firms in India and China respectively and identify the roles played in these relational networks by the particularly characteristic institutions in each case. We find greatly different social network structures in each case with some support in these relational dimensions for their distinctive features of governance. Further, the social network metrics allow us to considerably refine proxies for political interference, managerial entrenchment and institutional control used in earlier econometric analysis.

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This study investigated coping strategies, conversation tactics, and marital interaction in acquired profound hearing loss (APHL) and compared emotionally stable (n = 15) and emotionally distressed (n = 7) participants. Nominated family members were assessed on most measures. Comparisons were also made in the subgroup of married participants. A combined distress criterion was derived from scores on standardized measures of anxiety, depression, hearing handicap, and post-traumatic stress. Groups were compared on the Ways-of-Coping Checklist, a newly devised measure of conversation tactics, and on the Couple Behaviour Report. It was found that distressed APHL participants were more likely to cope through avoidance, self-blame, and wishful thinking, and they used more avoidant tactics in conversation. The coping profile of family members did not differentiate distress groups. However, there was some indication of greater employment of coercive tactics by family members of distressed participants. The results are consistent with the view that the coping style of a person with APHL and the nature of their conversational interactions with family members contribute to their level of distress. Implications for audiological rehabilitation are discussed.

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This study presents a fully coupled temperature–displacement finite element modelling of the injection stretch-blow moulding (ISBM) process of polyethylene terephthalate (PET) bottles using ABAQUS with a view to optimising the process conditions. A physically-based material model (Buckley model) was used to predict the mechanical behaviour of PET at temperatures slightly above its glass transition temperature. A model incorporating heat transfer between the stretch rod, the preform and the mould was built using axisymmetric solid elements. Extensive finite element analyses were carried out to predict the deformation, the distribution and history of strain and temperature during ISBM of a 20 g–330 ml bottle, which was made in an in situ test on a Sidel SB06 machine. Comparisons of numerical results with the measurements demonstrate that the model can satisfactorily model the sidewall thickness and material distributions. It is also shown that significant non-linear differentials exist in temperature and strain in both bottle thickness and length directions during the process. This justifies the employment of a volume approach to accurately predict the final mechanical properties of the bottles governed by the orientation and crystallinity which are highly temperature and strain dependent.

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Yeasts and filamentous fungi are beginning to emerge as significant microbial pathogens in patients with cystic fibrosis (CF), particularly in relation to allergic-type responses, as seen in patients with allergic bronchopulmonary aspergillosis (ABPA), Aspergillus bronchitis and in invasive fungal disease in lung transplant patients. Four fungal media were compared in this study, including Sabouraud Dextrose Agar (SDA) and Medium B, with and without the addition of selective antibiotics, where antibiotic-supplemented media were designated with (+). These media were compared for their ability to suppress contaminating, mainly Gram-ve pathogens, in CF sputa (Pseudomonas aeruginosa, Burkholderia cepacia complex [BCC] organisms) and to enhance the growth of fungi present in CF sputum. Medium B consisted of glucose (16.7 g/l), agar (20 g/l), yeast extract (30 g/l) and peptone (6.8 g/l) at pH 6.3 and both SDA(+) and Medium B+ were supplemented with cotrimethoxazole, 128 mg/l; chloramphenicol, 50 mg/l; ceftazidime, 32 mg/l; colistin, 24 mg/l). Employment of SDA(+) or Medium B+ allowed an increase in specificity in the detection of yeasts and moulds, by 42.8% and 39.3%, respectively, over SDA when used solely. SDA(+) had a greater ability than Medium B+ to suppress bacterial growth from predominantly Gram-ve co-colonisers. This is a significant benefit when attempting to detect and isolate fungi from the sputum of CF patients, as it largely suppressed any bacterial growth, with the exception of the BCC organisms, thus allowing for an increased opportunity to detect target fungal organisms in sputum and represented a significant improvement over the commercial medium (SDA), which is currently used. Overall, both novel selective media were superior in their ability to suppress bacteria in comparison with the commercially available SDA medium, which is routinely employed in most clinical microbiology diagnostic laboratories presently. Alternatively, Medium B+ had a great ability to grow fungi than SDA(+) and when employed together, the specificity of combined use was 82%, with a sensitivity for yeasts, filamentous fungi, and combined overall fungi of 96.0%, 92.3% and 96.0%, respectively. Overall, when employing one fungal selective medium for the routine detection of yeasts and filamentous fungi in the sputum of CF patients, we would recommend employment of Medium B+. However, we would recommend the combined employment of SDA(+) and Medium B+, in order to synergistically isolate and detect the greatest number of fungi present in CF sputa. (C) 2008 European Cystic Fibrosis Society. Published by Elsevier B.V All rights reserved.

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Cystic fibrosis (CF) patients may suffer increased morbidity and mortality through colonisation, allergy and invasive infection from fungi. The black yeast, Exophiala dermatitidis (synonym Wangiella dermatitidis) has been found with increasing frequency in sputum specimens of CF patients, with reported isolation rates ranging from 1.1 to 15.7%. At present, no diagnostic PCR exists to aid with the clinical laboratory detection and identification of this organism. A novel species-specific PCR-based assay was developed for the detection of E. dermatitidis, based on employment of rDNA operons and interspacer (ITS) regions between these rDNA operons. Two novel primers, (designated ExdF & ExdR) were designed in silico with the aid of computer-aided alignment software and with the alignment of multiple species of Exophiala, as well as with other commonly described yeasts and filamentous fungi within CF sputum, including Candida. Aspergillus and Scedosporium. An amplicon of approximately 455 by was generated, spanning the partial ITS I region - the complete 5.8S rDNA region - partial ITS2 region, employing ExdF (forward primer [16-mer], 5'-CCG CCT ATT CAG GTC C-3' and ExdR (reverse primer [16-mer], 5'-TCT CTC CCA CTC CCG C-3', was employed and optimised on extracted genomic DNA from a well characterised culture of E. dermatitidis, as well as with high quality genomic DNA template from a further 16 unrelated fungi, including Candida albicans, C. dubliniensis, C. parapsilosis, C. glabrata, Scedosporium apiospermum, Penicillium sp., Aspergillus fumigatus, Aspergillus versicolor, Pichia guilliermondii, Rhodotorula sp., Trichosporon sp., Aureobasidium pullulans, Fusarium sp., Mucor hiemalis, Bionectria ochroleuca, Gibberella pulicaris. Results demonstrated that only DNA from E. dermatitidis gave an amplification product of the expected sire, whilst none of the other fungi were amplifiable. Subsequent employment of this primer pair detected this yeast from mycological cultures from 2/50 (4%) adult CF patients. These two patients were the only patients who were previously shown to have a cultural history of E. dermatitidis from their sputum. E. dermatitidis is a slow-growing fungus, which usually takes up to two weeks to culture in the microbiology laboratory and therefore is slow to detect conventionally, with the risk of bacterial overgrowth from common co-habiting pan- and multiresistant bacterial pathogens from sputum. namely Pseudomonas aeruginosa and Burkholderia cepacia complex organisms, hence this species-specific PCR assay may help detect this organism from CF sputum more specifically and rapidly. Overall, employment of this novel assay nay help in the understanding of the occurrence. aetiology and epidemiology of E. dermatitidis, as an emerging fungal agent in patients with CF. (C) 2008 European Cystic Fibrosis Society. Published by Elsevier B.V. All rights reserved.

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Predicable and controlled degradation is not only central to the accurate delivery of bioactive agents and drugs, it also plays a vital role in key aspects of bone tissue engineering. The work addressed in this paper investigates the utilisation of e-beam irradiation in order to achieve a controlled (surface) degradation profile. This study focuses on the modification of commercially and clinically relevant materials, namely poly(L-lactic acid) (PLLA), poly(L-lactide-hydroxyapatite) (PLLA-HA), poly(L-lactide-glycolide) co-polymer (PLG) and poly(L-lactide-DL-lactide) co-polymer (PLDL). Samples were subjected to irradiation treatments using a 0.5 MeV electron beam with delivered surface doses of 150 and 500 kGy. In addition, an acrylic attenuation shield was used for selected samples to control the penetration of the e-beam. E-beam irradiation induced chain scission in all polymers, as characterized by reduced molecular weights and glass transition temperatures (T-g). Irradiation not only produced changes in the physical properties of the polymers but also had associated effects on surface erosion of the materials during hydrolytic degradation. Moreover, the extent to which both mechanical and hydrolytic degradation was observed is synonymous with the estimated penetration of the beam (as controlled by the employment of an attenuation shield). (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

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Since the 1980s, there has existed a field of scholarly inquiry into a range of phenomena termed New Age. The relative lack of ethnographic studies in this field was identified several years ago, in response to research that focused merely on the discourses within alleged key writings. However, the employment of ethnographic methods does not by itself resolve the problems inherent in other modes of research; attention also has to be paid to how ethnography is used in practice. This article examines ethnographies of the New Age in terms of the extent to which they contextualize data within their immediate social frames, by paying attention to actors’ practices and interactions, and to the ways in which beliefs and discourses are constructed and contested. The article demonstrates the strong tendency among New Age ethnographic studies to veer from ‘the social’ and to rest instead on analytically problematic conceptualizations of agency. It argues that epistemological revision is required to form the basis of a more sociologically adequate understanding of the phenomena addressed.