Measurement of carotenoid levels in human serum and a catalog of the lutein conformation populations from semi-empirical calculations

Lutein is a principal constituent of the human macular pigment. This study is composed of two projects. The first studies the conformational geometries of lutein and its potential adaptability in biological systems. The second is a study of the response of human subjects to lutein supplements. Using semi-empirical parametric method 3 (PM3) and density functional theory with the B3LYP/6-31G* basis set, the relative energies of s- cis conformers of lutein were determined. All 512 s-cis conformers were calculated with PM3. A smaller, representative group was also studied using density functional theory. PM3 results were correlated systematically to B3LYP values and this enables the results to be calibrated. The relative energies of the conformers range from 1-30 kcal/mole, and many are dynamically accessible at normal temperatures. Four commercial formulations containing lutein were studied. The serum and macular pigment (MP) responses of human subjects to these lutein supplements with doses of 9 or 20 mg/day were measured, relative to a placebo, over a six month period. In each instance, lutein levels in serum increased and correlated with MP increases. The results demonstrate that responses are significantly dependent upon formulation and that components other than lutein have an important influence serum response.

Building Regional Security: Cooperation in the 21st Century: The Case of the Caribbean Regional Security System [RSS]

Small states that lack capacity and act on their own may fall victim to international and domestic terrorism, transnational organized crime or criminal gangs. The critical issue is not whether small Caribbean states should cooperate in meeting security challenges, but it is rather in what manner, and by which mechanisms can they overcome obstacles in the way of cooperation. The remit of the Regional Security System (RSS) has expanded dramatically, but its capabilities have improved very slowly. The member governments of the RSS are reluctant to develop military capacity beyond current levels since they see economic and social development and disaster relief as priorities, requiring little investment in military hardware. The RSS depends on international donors such as the USA, Canada, Great Britain, and increasingly China to fund training programs, maintain equipment and acquire material. In the view of most analysts, an expanded regional arrangement based on an RSS nucleus is not likely in the foreseeable future. Regional political consensus remains elusive and the predominance of national interests over regional considerations continues to serve as an obstacle to any CARICOM wide regional defense mechanism. Countries in the Caribbean, including the members of the RSS, have to become more responsible for their own security from their own resources. While larger CARICOM economies can do this, it would be difficult for most OECS members of the RSS to do the same. The CARICOM region including the RSS member countries, have undertaken direct regional initiatives in security collaboration. Implementation of the recommendations of the Regional Task Force on Crime and Security (RTFCS) and the structure and mechanisms created for the staging of the Cricket World Cup (CWC 2007) resulted in unprecedented levels of cooperation and permanent legacy institutions for the regional security toolbox. The most important tier of security relationships for the region is the United States and particularly USSOUTHCOM. The Caribbean Basin Security Initiative [CBSI] in which the countries of the RSS participate is a useful U.S. sponsored tool to strengthen the capabilities of the Caribbean countries and promote regional ownership of security initiatives. Future developments under discussion by policy makers in the Caribbean security environment include the granting of law enforcement authority to the military, the formation of a single OECS Police Force, and the creation of a single judicial and law enforcement space. The RSS must continue to work with its CARICOM partners, as well as with the traditional “Atlantic Powers” particularly Canada, the United States and the United Kingdom to implement a general framework for regional security collaboration. Regional security cooperation should embrace wider traditional and non-traditional elements of security appropriate to the 21st century. Security cooperation must utilize to the maximum the best available institutions, mechanisms, techniques and procedures already available in the region. The objective should not be the creation of new agencies but rather the generation of new resources to take effective operations to higher cumulative levels. Security and non-security tools should be combined for both strategic and operational purposes. Regional, hemispheric, and global implications of tactical and operational actions must be understood and appreciated by the forces of the RSS member states. The structure and mechanisms, created for the staging of Cricket World Cup 2007 should remain as legacy institutions and a toolbox for improving regional security cooperation in the Caribbean. RSS collaboration should build on the process of operational level synergies with traditional military partners. In this context, the United States must be a true partner with shared interests, and with the ability to work unobtrusively in a nationalistic environment. Withdrawal of U.S. support for the RSS is not an option.

Assessment of the occurrence and potential risks of antibiotics and their metabolites in South Florida waters using liquid chromatography tandem mass spectrometry

An automated on-line SPE-LC-MS/MS method was developed for the quantitation of multiple classes of antibiotics in environmental waters. High sensitivity in the low ng/L range was accomplished by using large volume injections with 10-mL of sample. Positive confirmation of analytes was achieved using two selected reaction monitoring (SRM) transitions per antibiotic and quantitation was performed using an internal standard approach. Samples were extracted using online solid phase extraction, then using column switching technique; extracted samples were immediately passed through liquid chromatography and analyzed by tandem mass spectrometry. The total run time per each sample was 20 min. The statistically calculated method detection limits for various environmental samples were between 1.2 and 63 ng/L. Furthermore, the method was validated in terms of precision, accuracy and linearity. ^ The developed analytical methodology was used to measure the occurrence of antibiotics in reclaimed waters (n=56), surface waters (n=53), ground waters (n=8) and drinking waters (n=54) collected from different parts of South Florida. In reclaimed waters, the most frequently detected antibiotics were nalidixic acid, erythromycin, clarithromycin, azithromycin trimethoprim, sulfamethoxazole and ofloxacin (19.3-604.9 ng/L). Detection of antibiotics in reclaimed waters indicates that they can't be completely removed by conventional wastewater treatment process. Furthermore, the average mass loads of antibiotics released into the local environment through reclaimed water were estimated as 0.248 Kg/day. Among the surface waters samples, Miami River (reaching up to 580 ng/L) and Black Creek canal (up to 124 ng/L) showed highest concentrations of antibiotics. No traces of antibiotics were found in ground waters. On the other hand, erythromycin (monitored as anhydro erythromycin) was detected in 82% of the drinking water samples (n.d-66 ng/L). The developed approach is suitable for both research and monitoring applications.^ Major metabolites of antibiotics in reclaimed wates were identified and quantified using high resolution benchtop Q-Exactive orbitrap mass spectrometer. A phase I metabolite of erythromycin was tentatively identified in full scan based on accurate mass measurement. Using extracted ion chromatogram (XIC), high resolution data-dependent MS/MS spectra and metabolic profiling software the metabolite was identified as desmethyl anhydro erythromycin with molecular formula C36H63NO12 and m/z 702.4423. The molar concentration of the metabolite to erythromycin was in the order of 13 %. To my knowledge, this is the first known report on this metabolite in reclaimed water. Another compound acetyl-sulfamethoxazole, a phase II metabolite of sulfamethoxazole was also identified in reclaimed water and mole fraction of the metabolite represent 36 %, of the cumulative sulfamethoxazole concentration. The results were illustrating the importance to include metabolites also in the routine analysis to obtain a mass balance for better understanding of the occurrence, fate and distribution of antibiotics in the environment. ^ Finally, all the antibiotics detected in reclaimed and surface waters were investigated to assess the potential risk to the aquatic organisms. The surface water antibiotic concentrations that represented the real time exposure conditions revealed that the macrolide antibiotics, erythromycin, clarithromycin and tylosin along with quinolone antibiotic, ciprofloxacin were suspected to induce high toxicity to aquatic biota. Preliminary results showing that, among the antibiotic groups tested, macrolides posed the highest ecological threat, and therefore, they may need to be further evaluated with, long-term exposure studies considering bioaccumulation factors and more number of species selected. Overall, the occurrence of antibiotics in aquatic environment is posing an ecological health concern.^

Israel, You Rascals

Mark Steel started doing stand-up in 1982 in England, around the circuit of bizarre gigs, going on after jugglers and escapologists and people that banged nails into their ear. Then came the Comedy Store and Jongleurs and getting bottled off at The Tunnel, and then a regular slot on Radio 4′s Loose Ends, where he met Joseph Heller, Christopher Lee and Gary Glitter. He did 4 series of ‘The Mark Steel Solution’, one for Radio 5 and the others on Radio 4, and a radio series about cricket, which provoked a whole page of fury in the Daily Express. He presented three series of a sports programme called ‘Extra Time’ which he was very proud of, especially as it went out on Tuesday nights on Radio 5 to possibly no listeners whatsoever. Then there was four series of the lectures on Radio 4, a book called ‘It’s Not a Runner Bean’, another one called ‘Reasons to be Cheerful’, and 3 television series of the lectures on BBC 4 and BBC 2. He has done weekly columns in Socialist Worker, the Guardian and the Independent. He has written a book called ‘Vive le Revolution’, and has been on various panel shows like Have I Got News For You and QI, and on Room 101, and on Question Time he says that he “got very confused when I insulted a member of the Tory shadow cabinet, and afterwards he said I was splendid and invited me for a drink.” And he’s spoken at lots of demonstrations and union meetings and protests, and appeared at quite a few benefits. This essay originally appeared on his website: http://marksteelinfo.com/blog/.

Assessment of the Occurrence and Potential Risks of Antibiotics and their Metabolites in South Florida Waters Using Liquid Chromatography Tandem Mass Spectrometry

An automated on-line SPE-LC-MS/MS method was developed for the quantitation of multiple classes of antibiotics in environmental waters. High sensitivity in the low ng/L range was accomplished by using large volume injections with 10-mL of sample. Positive confirmation of analytes was achieved using two selected reaction monitoring (SRM) transitions per antibiotic and quantitation was performed using an internal standard approach. Samples were extracted using online solid phase extraction, then using column switching technique; extracted samples were immediately passed through liquid chromatography and analyzed by tandem mass spectrometry. The total run time per each sample was 20 min. The statistically calculated method detection limits for various environmental samples were between 1.2 and 63 ng/L. Furthermore, the method was validated in terms of precision, accuracy and linearity. The developed analytical methodology was used to measure the occurrence of antibiotics in reclaimed waters (n=56), surface waters (n=53), ground waters (n=8) and drinking waters (n=54) collected from different parts of South Florida. In reclaimed waters, the most frequently detected antibiotics were nalidixic acid, erythromycin, clarithromycin, azithromycin trimethoprim, sulfamethoxazole and ofloxacin (19.3-604.9 ng/L). Detection of antibiotics in reclaimed waters indicates that they can’t be completely removed by conventional wastewater treatment process. Furthermore, the average mass loads of antibiotics released into the local environment through reclaimed water were estimated as 0.248 Kg/day. Among the surface waters samples, Miami River (reaching up to 580 ng/L) and Black Creek canal (up to 124 ng/L) showed highest concentrations of antibiotics. No traces of antibiotics were found in ground waters. On the other hand, erythromycin (monitored as anhydro erythromycin) was detected in 82% of the drinking water samples (n.d-66 ng/L). The developed approach is suitable for both research and monitoring applications. Major metabolites of antibiotics in reclaimed wates were identified and quantified using high resolution benchtop Q-Exactive orbitrap mass spectrometer. A phase I metabolite of erythromycin was tentatively identified in full scan based on accurate mass measurement. Using extracted ion chromatogram (XIC), high resolution data-dependent MS/MS spectra and metabolic profiling software the metabolite was identified as desmethyl anhydro erythromycin with molecular formula C36H63NO12 and m/z 702.4423. The molar concentration of the metabolite to erythromycin was in the order of 13 %. To my knowledge, this is the first known report on this metabolite in reclaimed water. Another compound acetyl-sulfamethoxazole, a phase II metabolite of sulfamethoxazole was also identified in reclaimed water and mole fraction of the metabolite represent 36 %, of the cumulative sulfamethoxazole concentration. The results were illustrating the importance to include metabolites also in the routine analysis to obtain a mass balance for better understanding of the occurrence, fate and distribution of antibiotics in the environment. Finally, all the antibiotics detected in reclaimed and surface waters were investigated to assess the potential risk to the aquatic organisms. The surface water antibiotic concentrations that represented the real time exposure conditions revealed that the macrolide antibiotics, erythromycin, clarithromycin and tylosin along with quinolone antibiotic, ciprofloxacin were suspected to induce high toxicity to aquatic biota. Preliminary results showing that, among the antibiotic groups tested, macrolides posed the highest ecological threat, and therefore, they may need to be further evaluated with, long-term exposure studies considering bioaccumulation factors and more number of species selected. Overall, the occurrence of antibiotics in aquatic environment is posing an ecological health concern.