Avoiding Carbothermal Reduction: Distillation of Alkoxysilanes from Biogenic, Green, and Sustainable Sources

The direct depolymerization of SiO2 to distillable alkoxysilanes has been explored repeatedly without success for 85 years as an alternative to carbothermal reduction (1900 °C) to Simet, followed by treatment with ROH. We report herein the base‐catalyzed depolymerization of SiO2 with diols to form distillable spirocyclic alkoxysilanes and Si(OEt)4. Thus, 2‐methyl‐2,4‐pentanediol, 2,2,4‐trimethyl‐1,3‐pentanediol, or ethylene glycol (EGH2) react with silica sources, such as rice hull ash, in the presence of NaOH (10 %) to form H2O and distillable spirocyclic alkoxysilanes [bis(2‐methyl‐2,4‐pentanediolato) silicate, bis(2,2,4‐trimethyl‐1,3‐pentanediolato) silicate or Si(eg)2 polymer with 5–98 % conversion, as governed by surface area/crystallinity. Si(eg)2 or bis(2‐methyl‐2,4‐pentanediolato) silicate reacted with EtOH and catalytic acid to give Si(OEt)4 in 60 % yield, thus providing inexpensive routes to high‐purity precipitated or fumed silica and compounds with single Si−C bonds.No detours: The base‐catalyzed depolymerization of SiO2 from different sources with diols led directly to distillable alkoxysilanes, including spirocyclic compounds, thus providing inexpensive routes to high‐purity silica and compounds with single Si−C bonds (see scheme): The alkoxysilanes could be converted either into Si(OEt)4 by treatment with EtOH and a catalytic amount of acid or into high‐purity precipitated (ppt) or fumed silica.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/137495/1/anie201506838-sup-0001-misc_information.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/137495/2/anie201506838.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/137495/3/anie201506838_am.pd

High Surface Area, Thermally Stable, Hydrophobic, Microporous, Rigid Gels Generated at Ambient from MeSi(OEt)3/(EtO)3SiCH2CH2Si(OEt)3 Mixtures by F−‐Catalyzed Hydrolysis

High surface area materials are of considerable interest for gas storage/capture, molecular sieving, catalyst supports, as well as for slow‐release drug‐delivery systems. We report here a very simple and fast route to very high surface area, mechanically robust, hydrophobic polymer gels prepared by fluoride‐catalyzed hydrolysis of mixtures of MeSi(OEt)3 and bis‐triethoxysilylethane (BTSE) at room temperature. These materials offer specific surface areas up to 1300 m2 g−1, peak pore sizes of 0.8 nm and thermal stabilities above 200 °C. The gelation times and surface areas can be controlled by adjusting the solvent volume (dichloromethane), percent fluoride (as nBu4NF or TBAF) and the BTSE contents. Polymers with other corners and linkers were also explored. These materials will further expand the materials databank for use in vacuum insulation panels and as thermally stable release and capture media.Simple fluoride‐catalyzed polymerization of methyltriethoxysilane and bistriethyoxysilylethane leads to the formation of amorphous materials with little post‐synthesis processing. These materials have surface areas up to 1300 m2 g−1, densities as low as 0.06 g mL−1 and non‐polar solvent uptake of about 500 % by mass.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/141416/1/chem201704941.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/141416/2/chem201704941_am.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/141416/3/chem201704941-sup-0001-misc_information.pd

Isolation and Characterization of Precise Dye/Dendrimer Ratios

Fluorescent dyes are commonly conjugated to nanomaterials for imaging applications using stochastic synthesis conditions that result in a Poisson distribution of dye/particle ratios and therefore a broad range of photophysical and biodistribution properties. We report the isolation and characterization of generation 5 poly(amidoamine) (G5 PAMAM) dendrimer samples containing 1, 2, 3, and 4 fluorescein (FC) or 6‐carboxytetramethylrhodamine succinimidyl ester (TAMRA) dyes per polymer particle. For the fluorescein case, this was achieved by stochastically functionalizing dendrimer with a cyclooctyne “click” ligand, separation into sample containing precisely defined “click” ligand/particle ratios using reverse‐phase high performance liquid chromatography (RP‐HPLC), followed by reaction with excess azide‐functionalized fluorescein dye. For the TAMRA samples, stochastically functionalized dendrimer was directly separated into precise dye/particle ratios using RP‐HPLC. These materials were characterized using 1 H and 19 F NMR spectroscopy, RP‐HPLC, UV/Vis and fluorescence spectroscopy, lifetime measurements, and MALDI. High definition : Two approaches for the formation of generation 5 PAMAM samples containing precise dye/dendrimer ratios are presented. The first approach, using direct separation based on dye hydrophobicity, generated a set of TAMRA‐containing dendrimers, and the second, using click chemistry, generated a set of fluorescein‐containing dendrimer (see figure).Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/106970/1/chem_201304854_sm_miscellaneous_information.pdfhttp://deepblue.lib.umich.edu/bitstream/2027.42/106970/2/4638_ftp.pd

Towards a better understanding of the benefits and risks of country food consumption using the case of walruses in Nunavik (Northern Quebec, Canada)

Food insecurity affects Inuit communities. One solution is to consume locally harvested foods, named country foods. However, some country foods are not eaten as often as before, and pressures including contaminants and environmental changes threaten the health of Arctic fauna, thus its suitability for local consumption. By combining Inuit Knowledge with laboratory data, our study assessed the benefits and risks of walrus consumption by Inuit in Nunavik, Québec, Canada. It aimed to increase understanding of: 1) the hunt of healthy Atlantic walruses (Odobenus rosmarus rosmarus); 2) the safe preparation of walruses; 3) the nutritional benefits and risks of consuming walruses. To do so, we interviewed 34 hunters and Elders from Nunavik. Levels of mercury, omega-3 polyunsaturated fatty acids and selenium were evaluated from locally harvested walruses. Through the Nunavik Trichinellosis Prevention Program, a total of 755 Atlantic walrus samples, collected between 1994 and 2013, were tested for Trichinella nativa. Information on botulism was reviewed. While interviews informed on how to select healthy walruses and prepare them for consumption, laboratory analyses revealed that walruses had elevated levels of omega-3 fatty acids and selenium but low levels of mercury compared to some other wildlife. Only 3% of the 755 walruses were infected with T. nativa. Most walruses' infections were found within individuals from the South East Hudson Bay stock, where Inuit have thus decided to stop hunting since mid-2000s. Finally, although the number of outbreaks of trichinellosis related to the consumption of walruses has significantly reduced in Nunavik, botulism could continue to be an issue when igunaq (i.e. aged walrus) is not properly prepared. With the support of the Nunavik Trichinellosis Prevention Program and transmission of Inuit knowledge on igunaq preparation, the consumption of Atlantic walruses has the potential to help address issues related to food insecurity in Nunavik in the future

Climate change effects on human health in a gender perspective: some trends in Arctic research

Background: Climate change and environmental pollution have become pressing concerns for the peoples in the Arctic region. Some researchers link climate change, transformations of living conditions and human health. A number of studies have also provided data on differentiating effects of climate change on women's and men's well-being and health. Objective: To show how the issues of climate and environment change, human health and gender are addressed in current research in the Arctic. The main purpose of this article is not to give a full review but to draw attention to the gaps in knowledge and challenges in the Arctic research trends on climate change, human health and gender. Methods: A broad literature search was undertaken using a variety of sources from natural, medical, social science and humanities. The focus was on the keywords. Results: Despite the evidence provided by many researchers on differentiating effects of climate change on well-being and health of women and men, gender perspective remains of marginal interest in climate change, environmental and health studies. At the same time, social sciences and humanities, and gender studies in particular, show little interest towards climate change impacts on human health in the Arctic. As a result, we still observe the division of labour between disciplines, the disciplinary-bound pictures of human development in the Arctic and terminology confusion. Conclusion: Efforts to bring in a gender perspective in the Arctic research will be successful only when different disciplines would work together. Multidisciplinary research is a way to challenge academic/disciplinary homogeneity and their boundaries, to take advantage of the diversity of approaches and methods in production of new integrated knowledge. Cooperation and dialogue across disciplines will help to develop adequate indicators for monitoring human health and elaborating efficient policies and strategies to the benefit of both women and men in the Arctic

Indicators of ocean health and human health: developing a research and monitoring framework

This is the final version of the article. Available from NIEHS via the DOI in this record.We need to critically assess the present quality of the marine ecosystem, especially the connection between ecosystem change and threats to human health. In this article we review the current state of indicators to link changes in marine organisms with eventual effects to human health, identify research opportunities in the use of indicators of ocean and human health, and discuss how to establish collaborations between national and international governmental and private sector groups. We present a synthesis of the present state of understanding of the connection between ocean health and human health, a discussion of areas where resources are required, and a discussion of critical research needs and a template for future work in this field. To understand fully the interactions between ocean health and human health, programs should be organized around a "models-based" approach focusing on critical themes and attributes of marine environmental and public health risks. Given the extent and complex nature of ocean and human health issues, a program networking across geographic and disciplinary boundaries is essential. The overall goal of this approach would be the early detection of potential marine-based contaminants, the protection of marine ecosystems, the prevention of associated human illness, and by implication, the development of products to enhance human well-being. The tight connection between research and monitoring is essential to develop such an indicator-based effort.This work was funded by the National Institute of Environmental Health Sciences, the Intergovernmental Oceanographic Commission (UNESCO), and the Bermuda Biological Station for Research, Inc. (contribution 1615)

Impacts of traditional food consumption advisories: Compliance, changes in diet and loss of confidence in traditional foods

<p>Abstract</p> <p>Background</p> <p>Food consumption advisories are often posted when industrial activities are expected to affect the quality and availability of traditional foods used by First Nations. We were recently involved in a project and asked to summarize details regarding the impacts of traditional food consumption advisories with respect to compliance, broader changes in diet and loss of confidence in traditional foods by people.</p> <p>Methods</p> <p>Our review was not conducted as a formal systematic comprehensive review; rather, we focused on primary and grey literature presenting academic, health practitioner and First Nations viewpoints on the topic available from literature databases (i.e., PubMed, Web of Knowledge^SM) as well as the internet search engine Google. Some information came from personal communications.</p> <p>Results</p> <p>Our overview suggests that when communicated effectively and clearly, and when community members are involved in the process, consumption advisories can result in a decrease in contaminant load in people. On the other hand, consumption advisories can lead to cultural loss and have been linked to a certain amount of social, psychological, nutritional, economic and lifestyle disruption. In some cases, communities have decided to ignore consumption advisories opting to continue with traditional lifestyles believing that the benefits of doing so outweigh the risk of following advisories.</p> <p>Conclusions</p> <p>We identified that there are both positive and negative aspects to the issuance of traditional food consumption advisories. A number of variables need to be recognized during the development and implementation of advisories in order to ensure a balance between human health, maintenance of cultures and industrial activity.</p