Assignment of absolute configuration of cyclic secondary amines by NMR techniques using Mosher's method: a general procedure exemplified with (-)-isoanabasine

A general procedure to determine the absolute configuration of cyclic secondary amines with Mosher's NMR method is demonstrated, with assignment of absolute configuration of isoanabasine as an example. Each Mosher amide can adopt two stable conformations (named rotamers) caused by hindered rotation around amide C-N bond. Via a three-step structural analysis of four rotamers, the absolute configuration of (-)-isoanabasine is deduced to be (R) on the basis of Newman projections, which makes it easy to understand and clarify the application of Mosher's method to cyclic secondary amines. Furthermore, it was observed that there was an unexpected ratio of rotamers of Mosher amide derived from (R)-isoanabasine and (R)-Mosher acid. This phenomenon implied that it is necessary to distinguish the predominant rotamer from the minor one prior to determining the absolute configuration while using this technique.

A one-pot procedure to prepare S-protected 4-iodothiophenols

By means of non-aqueous reduction of pipsyl chloride followed by treatment with K2CO3 and then reacting with acetyl chloride or benzyl chloride, S-acetyl/benzyl -4-iodothiophenols were obtained in a one-pot procedure with yield as high as 90%. These S-protected arenethiols are very important intermediates to synthesize self-assembled molecular wires.

Study on a novel polyimide precursor prepared by a modified polymerization of monomeric reactants (MPMR) procedure

A novel polyimide precursor based on the dimethyl ester of 3,3',4,4'-biphenyltetracarboxylic acid, 4,4'-methylene dianiline and the monomethyl ester of 5-norbornene-2,3-dicarboxylic acid (BPDE/MDA/NE) was prepared by a modified polymerization of monomeric reactants (PMR) approach (MPMR). The composition of the precursor was quantitatively characterized by means of FTIR, HPLC and GC. The fractions of imide, amic ester and amic acid units in the precursor, typically prepared by refluxing in 1,4-dioxane for 2 h, were 33.7, 30.8 and 1.1 mol-%, respectively. The portion of free MDA was 3.34 wt.-% as determined by HPLC.

A one-pot procedure to prepare ethynylferrocene and iodoethynylferrocene

Ethynylferrocene and iodoethynylferrocene were prepared in high yield as 88-90% through a one-pot procedure. 1, 1'-diiodoferrocenylene was in-situ prepared from reaction of CHI3 PPh3, t-BuOK and ferrocenecarboxaldehyde, further reaction with t-BuOK or n-BuLi gave the title compounds.

Improved procedure for preparation of covalently bonded cellulose tris-phenylcarbamate chiral stationary phases

The classical method for preparation of covalently boned cellulose derivative chiral stationary phases (CSP) with diisocyanate as spacer was improved. Diisocyanate was firstly allowed to react with 3-aminopropyltriethoxysilane, and the resulting product was then applied as the spacer reagent to immobilize cellulose derivatives onto silica gel. Influences of the amount and the length of the spacer on the optical resolution ability of the CSP were investigated. Comparing improved procedure to classical diisocyanate method, the cross-linking between the glucose units of the cellulose derivatives was avoided to the most extent. With the improved procedure, regio-nonselective ways could be adopted to prepare covalently bonded CSP, which showed an advantage for the rapid preparation.

Shifting the Burden of HIV/AIDS

As the economic burden of HIV/AIDS increases in sub-Saharan Africa, the allocation of the burden among levels and sectors of societies is changing. The private sector has greater scope than government, households, or NGOs to avoid the economic burden of AIDS, and a systematic shifting of the burden away from the private sector is underway. Common practices that shift the AIDS burden from businesses to households and government include pre-employment screening, reduced employee benefits, restructured employment contracts, outsourcing of less skilled jobs, selective retrenchments, and changes in production technologies. In South Africa, more than two thirds of large employers have reduced health care benefits or required larger contributions by employees. Most firms have replaced defined benefit retirement funds, which expose the firm to large annual costs but provide long-term support for families, with defined contribution funds, which eliminate firm risk but provide little to families of younger workers who die of AIDS. Contracting out of previously permanent jobs also shields firms from costs while leaving households and government to care for affected workers and their families. Many of these changes are responses to globalization and would have occurred in the absence of AIDS, but they are devastating for employees with HIV/AIDS. This paper argues that the shifting of the economic burden of AIDS is a predictable response by business to which a thoughtful public policy response is needed. Countries should make explicit decisions about each sector’s responsibilities if a socially desirable allocation is to be achieved.

Measuring Bottleneck Link Speed in Package-Switched Networks

The quality of available network connections can often have a large impact on the performance of distributed applications. For example, document transfer applications such as FTP, Gopher and the World Wide Web suffer increased response times as a result of network congestion. For these applications, the document transfer time is directly related to the available bandwidth of the connection. Available bandwidth depends on two things: 1) the underlying capacity of the path from client to server, which is limited by the bottleneck link; and 2) the amount of other traffic competing for links on the path. If measurements of these quantities were available to the application, the current utilization of connections could be calculated. Network utilization could then be used as a basis for selection from a set of alternative connections or servers, thus providing reduced response time. Such a dynamic server selection scheme would be especially important in a mobile computing environment in which the set of available servers is frequently changing. In order to provide these measurements at the application level, we introduce two tools: bprobe, which provides an estimate of the uncongested bandwidth of a path; and cprobe, which gives an estimate of the current congestion along a path. These two measures may be used in combination to provide the application with an estimate of available bandwidth between server and client thereby enabling application-level congestion avoidance. In this paper we discuss the design and implementation of our probe tools, specifically illustrating the techniques used to achieve accuracy and robustness. We present validation studies for both tools which demonstrate their reliability in the face of actual Internet conditions; and we give results of a survey of available bandwidth to a random set of WWW servers as a sample application of our probe technique. We conclude with descriptions of other applications of our measurement tools, several of which are currently under development.

Measuring Bottleneck Bandwidth of Targeted Path Segments

Accurate measurement of network bandwidth is crucial for flexible Internet applications and protocols which actively manage and dynamically adapt to changing utilization of network resources. These applications must do so to perform tasks such as distributing and delivering high-bandwidth media, scheduling service requests and performing admission control. Extensive work has focused on two approaches to measuring bandwidth: measuring it hop-by-hop, and measuring it end-to-end along a path. Unfortunately, best-practice techniques for the former are inefficient and techniques for the latter are only able to observe bottlenecks visible at end-to-end scope. In this paper, we develop and simulate end-to-end probing methods which can measure bottleneck bandwidth along arbitrary, targeted subpaths of a path in the network, including subpaths shared by a set of flows. As another important contribution, we describe a number of practical applications which we foresee as standing to benefit from solutions to this problem, especially in emerging, flexible network architectures such as overlay networks, ad-hoc networks, peer-to-peer architectures and massively accessed content servers.

Do technology shocks drive hours up or down? A little evidence from an agnostic procedure

This paper analyzes the robustness of the estimate of a positive productivity shock on hours to the presence of a possible unit root in hours. Estimations in levels or in first differences provide opposite conclusions. We rely on an agnostic procedure in which the researcher does not have to choose between a specification in levels or in first differences. We find that a positive productivity shock has a negative impact effect on hours, but the effect is much shorter lived, and disappears after two quarters. The effect becomes positive at business-cycle frequencies, although it is not significant. © 2005 Cambridge University Press.

Variation in the type and frequency of postoperative invasive Staphylococcus aureus infections according to type of surgical procedure.

OBJECTIVE: To determine the epidemiological characteristics of postoperative invasive Staphylococcus aureus infection following 4 types of major surgical procedures.design. Retrospective cohort study. SETTING: Eleven hospitals (9 community hospitals and 2 tertiary care hospitals) in North Carolina and Virginia. PATIENTS: Adults undergoing orthopedic, neurosurgical, cardiothoracic, and plastic surgical procedures. METHODS: We used previously validated, prospectively collected surgical surveillance data for surgical site infection and microbiological data for bloodstream infection. The study period was 2003 through 2006. We defined invasive S. aureus infection as either nonsuperficial incisional surgical site infection or bloodstream infection. Nonparametric bootstrapping was used to generate 95% confidence intervals (CIs). P values were generated using the Pearson chi2 test, Student t test, or Wilcoxon rank-sum test, as appropriate. RESULTS: In total, 81,267 patients underwent 96,455 procedures during the study period. The overall incidence of invasive S. aureus infection was 0.47 infections per 100 procedures (95% CI, 0.43-0.52); 227 (51%) of 446 infections were due to methicillin-resistant S.aureus. Invasive S. aureus infection was more common after cardiothoracic procedures (incidence, 0.79 infections per 100 procedures [95%CI, 0.62-0.97]) than after orthopedic procedures (0.37 infections per 100 procedures [95% CI, 0.32-0.42]), neurosurgical procedures (0.62 infections per 100 procedures [95% CI, 0.53-0.72]), or plastic surgical procedures (0.32 infections per 100 procedures [95% CI, 0.17-0.47]) (P < .001). Similarly, S. aureus bloodstream infection was most common after cardiothoracic procedures (incidence, 0.57 infections per 100 procedures [95% CI, 0.43-0.72]; P < .001, compared with other procedure types), comprising almost three-quarters of the invasive S. aureus infections after these procedures. The highest rate of surgical site infection was observed after neurosurgical procedures (incidence, 0.50 infections per 100 procedures [95% CI, 0.42-0.59]; P < .001, compared with other procedure types), comprising 80% of invasive S.aureus infections after these procedures. CONCLUSION: The frequency and type of postoperative invasive S. aureus infection varied significantly across procedure types. The highest risk procedures, such as cardiothoracic procedures, should be targeted for ongoing preventative interventions.

Shifting Loyalties: World War I and the Conflicted Politics of Patriotism in the British Caribbean

This dissertation examines how the crisis of World War I impacted imperial policy and popular claims-making in the British Caribbean. Between 1915 and 1918, tens of thousands of men from the British Caribbean volunteered to fight in World War I and nearly 16,000 men, hailing from every British colony in the region, served in the newly formed British West Indies Regiment (BWIR). Rousing appeals to imperial patriotism and manly duty during the wartime recruitment campaigns and postwar commemoration movement linked the British Empire, civilization, and Christianity while simultaneously promoting new roles for women vis-à-vis the colonial state. In Jamaica and Trinidad and Tobago, the two colonies that contributed over seventy-five percent of the British Caribbean troops, discussions about the meaning of the war for black, coloured, white, East Indian, and Chinese residents sparked heated debates about the relationship among race, gender, and imperial loyalty.

To explore these debates, this dissertation foregrounds the social, cultural, and political practices of BWIR soldiers, tracing their engagements with colonial authorities, military officials, and West Indian civilians throughout the war years. It begins by reassessing the origins of the BWIR, and then analyzes the regional campaign to recruit West Indian men for military service. Travelling with newly enlisted volunteers across the Atlantic, this study then chronicles soldiers' multi-sited campaign for equal status, pay, and standing in the British imperial armed forces. It closes by offering new perspectives on the dramatic postwar protests by BWIR soldiers in Italy in 1918 and British Honduras and Trinidad in 1919, and reflects on the trajectory of veterans' activism in the postwar era.

This study argues that the racism and discrimination soldiers experienced overseas fueled heightened claims-making in the postwar era. In the aftermath of the war, veterans mobilized collectively to garner financial support and social recognition from colonial officials. Rather than withdrawing their allegiance from the empire, ex-servicemen and civilians invoked notions of mutual obligation to argue that British officials owed a debt to West Indians for their wartime sacrifices. This study reveals the continued salience of imperial patriotism, even as veterans and their civilian allies invoked nested local, regional, and diasporic loyalties as well. In doing so, it contributes to the literature on the origins of patriotism in the colonial Caribbean, while providing a historical case study for contemporary debates about "hegemonic dissolution" and popular mobilization in the region.

This dissertation draws upon a wide range of written and visual sources, including archival materials, war recruitment posters, newspapers, oral histories, photographs, and memoirs. In addition to Colonial Office records and military files, it incorporates previously untapped letters and petitions from the Jamaica Archives, National Archives of Trinidad and Tobago, Barbados Department of Archives, and US National Archives.

Shifting ranges and conservation challenges for lemurs in the face of climate change.

Geospatial modeling is one of the most powerful tools available to conservation biologists for estimating current species ranges of Earth's biodiversity. Now, with the advantage of predictive climate models, these methods can be deployed for understanding future impacts on threatened biota. Here, we employ predictive modeling under a conservative estimate of future climate change to examine impacts on the future abundance and geographic distributions of Malagasy lemurs. Using distribution data from the primary literature, we employed ensemble species distribution models and geospatial analyses to predict future changes in species distributions. Current species distribution models (SDMs) were created within the BIOMOD2 framework that capitalizes on ten widely used modeling techniques. Future and current SDMs were then subtracted from each other, and areas of contraction, expansion, and stability were calculated. Model overprediction is a common issue associated Malagasy taxa. Accordingly, we introduce novel methods for incorporating biological data on dispersal potential to better inform the selection of pseudo-absence points. This study predicts that 60% of the 57 species examined will experience a considerable range of reductions in the next seventy years entirely due to future climate change. Of these species, range sizes are predicted to decrease by an average of 59.6%. Nine lemur species (16%) are predicted to expand their ranges, and 13 species (22.8%) distribution sizes were predicted to be stable through time. Species ranges will experience severe shifts, typically contractions, and for the majority of lemur species, geographic distributions will be considerably altered. We identify three areas in dire need of protection, concluding that strategically managed forest corridors must be a key component of lemur and other biodiversity conservation strategies. This recommendation is all the more urgent given that the results presented here do not take into account patterns of ongoing habitat destruction relating to human activities.